Multimetallic Compounds and Nanoparticles Functionalised

Multimetallic Compounds and Nanoparticles

Functionalised with Transitional Metal Units for

Application in Catalysis

Khairil Anuar Jantan

Department of Chemistry Imperial College London

A thesis submitted for the degree of Doctor of Philosophy and the Diploma of

Imperial College London

2018

ii

Declaration

I declare that the work described in this thesis was carried out in accordance with the

regulations of Imperial College London The work is my own except where indicated

in the text and no part of the thesis was submitted previously for a degree at this or

any other university

iii

Statement of Copyright

Imperial College of Science Technology and Medicine

Department of Chemistry

Multimetallic Compounds and Nanoparticles Functionalised with Transitional Metal

Units for Application in Catalysis

copy 2018 Khairil Anuar Jantan

kjantan13imperialacuk

The copyright of this thesis rests with the author Unless otherwise indicated its

contents are licensed under a Creative Commons Attribution-NonCommercial 40

International Licence (CC BY-NC)

Under this licence you may copy and redistribute the material in any medium or

format You may also create and distribute modified versions of the work This is on

the condition that you credit the author and do not use it or any derivative works for

a commercial purpose

When reusing or sharing this work ensure you make the licence terms clear to others

by naming the licence and linking to the licence text Where a work has been adapted

you should indicate that the work has been changed and describe those changes

Please seek permission from the copyright holder for uses of this work that are not

included in this licence or permitted under UK Copyright Law

iv

Publications

bull Bifunctional Chalcogen Linkers for the Stepwise Generation of

Multimetallic Assemblies and Functionalized Nanoparticles

J A Robson F Gonzalez de Rivera K A Jantan M N Wenzel A J P White O Rossell and J D E T Wilton-Ely Inorg Chem 2016 55 12982ndash12996 DOI 101021acsinorgchem6b02409

bull The stepwise generation of multimetallic complexes based on a

vinylbipyridine linkage and their photophysical properties

A Toscani K A Jantan J B Hena J A Robson E J Parmenter V Fiorini A J P White S Stagni and J D E T Wilton-Ely Dalton Trans 2017 46 5558-5570 DOI 101039c6dt03810g

bull From Recovered Metal Waste to High-Performance Palladium Catalyst K A Jantan C Y Kwok K W Chan L Marchio A J P White P Deplano A Serpe and J D E T Wilton-Ely Green Chem 2017 19 5846ndash5853 DOI 101039c7gc02678a

v

Acknowledgements

It is impossible to accurately represent how genuinely grateful I am to all of my family

friends lab mates and especially my advisor Dr James Wilton-Ely Nothing in this

thesis would have been possible without each one of you Thank you

Dr James thank you for giving me the opportunity to work in your lab You were a

great advisor to me you always had enthusiasm for the chemistry even when it did

not want to cooperate Thank you for having my back teaching me and guiding me

within the chemistry community and encouraging me in my ambitions Your believing

in me as a chemist gives me the confidence to go forward and pursue my highest

ambitions Honestly words cannot express my gratitude

To everyone in the JWE Lab past and present- Thank you I consider myself very

lucky to have a lab that became a family for me Our lab is so much fun to work in and

be a part ofhellip from the outside we probably look crazy but they have no idea what

they are missing

I wish to express my sincere thanks to the following people whose input in this

research have made it possible to produce this thesis

Dr James Wilton-Ely Supervisor

Dr Lorenzo Magnon and Dr Margot Wenzel Postdoctoral researchers

Dr Andrew Rogers (West Brompton Hospital) TEM images

Dr Caterina Ware (Imperial College) TEMEDX

Dr Andrew White (Imperial College) Crystallography

vi

Dr Peter Haycock and Dr Dick Shepherd (Imperial College) NMR spectroscopy

I thank the Ministry of Higher Education of Malaysia and Universiti Teknologi Mara

(UiTM) for funding this PhD study and gratefully acknowledge the support and facilities

provided by the Department of Chemistry Imperial College London

Thanks to all my friends who have been steadfast in their support Nik Azhar Muzamir

Azizi Jamil and Nazaruddin listening patiently when I spoke about my research trying

their best to sound interested Finally I wish to extend my warmest thanks to my family

especially to my wife Zuraidah Jantan and our beloved daughters Sherylamiera and

Qalesya Adelia for their continual support understanding and words of

encouragement throughout my PhD and their invaluable prayers To my lovely

parents thanks for everything

vii

Abstract

The introduction (Chapter 1) provides an overview of the main topics encountered in

the thesis including the stepwise generation of multimetallic assemblies based on

different chelating ligands gold nanoparticles and surface functionalization palladium-

based catalysts (homogeneous and heterogeneous) This last part focuses on C-H

functionalization and Suzuki-Miyaura reactions reporting examples and dealing with

the recovery process and re-use of palladium from secondary sources

Chapter 2 outlines the stepwise generation of mono- bi- and multimetallic assemblies

based on different polyfunctional ligands including dicarboxylates pyridine derivatives

and dithiocarbamates The synthesis and characterisation of the novel complexes are

described along with the immobilisation of a ruthenium compound bearing a disulfide

ligand on the surface of gold and palladium nanoparticles

In the third Chapter the research focus shifts to the synthesis and characterisation of

mono- and bi-metallic novel palladium complexes bearing dithiocarbamate ligands In

addition the preparation of palladium dithiooxamide complexes derived from

secondary sources (spent catalytic converters) is described All the palladium

complexes were screened as potential homogeneous catalysts in the C-H activation

of benzo[h]quinoline and 8-methylquinoline The optimisation of the reaction

conditions by varying three different factors catalyst loading temperature and time is

tested and discussed

In Chapter 4 the use of simple and commercially available iodine and a

tetrabutylammonium salt as leaching agents in a palladium recovery process is

described The reactivity of bimetallic palladium complexes generated from the

process was then investigated in the C-H activation and Suzuki-Miyaura cross-

coupling reactions Furthermore a novel route to produce a variety Pd(II) catalyst via

ligand exchange reaction of bimetallic palladium complex with inexpensive phosphine

ligands is also presented These catalysts were tested using electron- donating and

withdrawing substrates in the cross-coupling reaction of phenylboronic acid

viii

Chapter 5 extends the scope of the research to heterogeneous catalysis The

preparation characterisation and immobilisation of novel palladium(II)

dithiocarbamate complexes are described along with construction of silica and silica-

coated iron-oxide nanoparticles and the support of the complex on the nanoparticles

The reactivity of unsupported and supported complexes toward C-H functionalization

of benzo[h]quinoline is discussed

The overall conclusions of the thesis are discussed in Chapter 6

Experimental procedures related to the synthesis characterisation and catalytic

studies of the compounds in Chapter 2 to 5 are detailed in Chapter 7

ix

Abbreviations

AuNP gold nanoparticle BTD 213-benzothiadiazole Cat Catalyst DMSO Dimethyl sulfoxide dppe 12-bis(diphenylphosphino)ethane dppf 11-Bis(diphenylphosphino)ferrocene dppm 11-bis(diphenylphosphino)methane DTC Dithiocarbamate EDX Energy Dispersive X-ray spectroscopy FT-IR Fourier transform infrared h Hour HSAB Hard and soft acid-base theory HC Hydrocarbons Hz Hertz ICP-OES Inductively Coupled Plasma-Optical Emission

Spectroscopy Ir Iridium IR Infrared JWE James Wilton-Ely KPF6 potassium hexafluorophosphate M transition metal Me2dazdtmiddot2I2 NN-dimethylperhydrodiazepine- 23-dithione diiodine

adduct min Minute MOFs metal-organic frameworks MNPrsquos Magnetic nanoparticles NHCs N-heterocyclic carbene NMs noble metals NMR Nuclear magnetic resonance pip Piperidine PGMs Platinum Group Metals ppm Part per million PPN bis(triphenylphosphine)iminium Py pyridine Pyr pyrene SOCDTC Standard Operating Condition of Pd-dithiocarbamate

complex SOCDTO Standard Operating Condition of Pd-DiThioOxamide

catalysts [TBA]I Tetrabutylammonium iodide TGA Thermogravimetric analysis TOAB tetraoctylammonium bromide TWCs three ways catalytic converter X activated ligand TEOS tetraethyl orthosilicate TEM Transmission Electron Microscopy US United States

x

Contents

Declaration ii

Statement of Copyright iii

Publication iv

Acknowledgement v

Abstract vii

Abbreviations ix

Contents x

1 Applications of multimetallic assemblies in catalysis

11 Generation of multimetallic complexes based on different chelating ligands

1

111 Why prepare multimetallic compounds 1

112 Dicarboxylates as linkers 2

113 Dithiocarbamates as linkers 3

114 Mixed donor ligands derived from carboxylate and pyridine as linkers

6

12 Gold nanoparticles and surface functionalisation 7

13 Applications of multimetallic assemblies in catalysis 9

131 Homogeneous vs heterogeneous catalysis 9

132 Oxidative functionalisation of C-H bonds 10

133 Suzuki-Miyaura cross-coupling reaction 16

134 Immobilised transition metals on surfaces 18

135 Catalysis by immobilised Pd(II) complexes 22

14 Recovery and re-use of Palladium 25

141 Palladium supply and demand 25

142 Recovery methods from secondary source of palladium 27

15 Thesis overview 29

xi

16 References 31

2 Stepwise construction of multimetallic assemblies and nanoparticle surface functionalisation

21 Background and significance 37

211 Aims and Objectives 38

22 Monometallic complexes bearing dithiocarbamate ligands 39

23 Heteromultimetallic complexes bearing a polyfunctional dicarboxylate ligand

45

24 Multimetallic complexes based on polyfunctional ligands (sulfur and nitrogen)

51

241 Synthesis of bi-and trimetallic complexes 51

242 Synthesis of bi- and trimetallic vinyl complexes 53

243 Synthesis of gold nanoparticles and surface functionalisation 57

244 Brust and Schiffrin method 58

245 Turkevich method 61

246 Palladium nanoparticle surface functionalisation 64

25 Conclusion 66

26 References 67

3 From recovered metal waste to high-performance palladium catalysts


311 Aims and objectives 72

32 Synthesis of dithiocarbamate and dithiooxamide complexes of palladium

73

321 Synthesis and characterisation of Pd(II) dithiocarbamate complexes

73

322 Structural discussion 75

323 Transformation of palladium metal to Pd(II) dithiooxamide products

79

33 Catalytic activity 80

331 Catalysis reaction conditions 82

xii

332 Initial catalytic studies 83

333 Standard operating conditions of palladium dithiocarbamate complexes (SOCDTC)

84

334 Extending the catalytic scope of Pd(II) dithiocarbamate complexes

87

34 Palladium dithiooxamide catalysts 88

341 Initial catalytic screening 89

342 Optimization of standard operating conditions for dithiooxamide catalysts (SOCDTO)

90

343 Isolated yield of the products 95

35 Conclusion 96

36 References 98

4 Generation of homogeneous palladium catalysts from secondary sources using simple ligands



42 Synthesis and characterisation of Pd(II) complexes derived from a secondary source

102

421 Synthesis and characterisation of palladium complexes 103

43 C-H functionalisation reaction catalysed by (TBA)2[Pd2I6] 105

431 Preliminary catalytic studies 106

432 C-H functionalization of benzo[h]quinoline employing (TBA)2[Pd2I6] as a catalyst

112

433 C-H functionalisation of 8-methylquinoline 114

434 Unsuccessful attempts at C-H functionalisation of other substrates

118


441 Catalysis reaction set up 119

442 Suzuki-Miyaura cross-coupling reaction with different palladium catalysts

121

45 Conclusion 128

46 References 130

xiii

5 Heterogenised molecular Pd(II) catalyst for C-H functionalisation



52 Synthesis and characterisation of palladium dithiocarbamate complexes

133

521 Synthesis of dithiocarbamate ligands 134

522 Synthesis of Pd(II) complexes bearing dithiocarbamate ligands 135

533 Crystal structure [(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36)

136

534 Crystal structure [(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6

(37) 138

53 Catalytic activity of heteroleptic palladium complexes 139

531 Optimisation of reaction conditions 141

532 Other alkoxy functionalisation of benzo[h]quinoline 142

54 Supported catalyst design 143

541 Synthesis of SiO2 nanoparticles 144

542 Synthesis of magnetic nanoparticles 145

543 Synthesis of SiO2Fe3O4 nanoparticles 147

544 Surface functionalisation of SiO2 nanoparticles with Pd complexes

148

545 Surface functionalisation of SiO2Fe3O4 nanoparticles with palladium complexes

149

546 Methoxylation of benzo[h]quinoline employing an immobilised palladium catalyst

152

55 Conclusion 154

56 References 156

6 Conclusions and future work

61 Conclusions 158

62 Future work 159

xiv

7 Experimental Detail

71 General considerations 161

72 Materials and methods 161

73 Synthesis of the compounds in Chapter 2

731 KS2CN(CH2py)2 (1) 163

732 [Au(S2CN(CH2py)2)(PPh3)] (2) 163

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3) 164

734 [Ru(S2CN(CH2py)2)(dppm)2](PF6) (4) 164

735 [Ru(CH=CHC6H4Me-4)(S2CN(CH2py)2)(CO)(PPh3)2] (5) 165

736 [Ru(CH=CHPyr-1)(S2CN(CH2py)2)(CO)(PPh3)2] (6) 165

737 [Ru(C(CequivCPh)=CHPh)(S2CN(CH2py)2)(CO)(PPh3)2] (7) 166

738 [Ni(S2C-N(CH2py)2)] (8) 166

739 [Ru(CH=CHC6H4Me-4)(CO)(PPh3)22(micro-dcbpy)] (9) 167

7310 [Ru(C(CequivCPh)=CHPh)(CO)(PPh3)22 (micro-dcbpy)] (10) 168

7311 [Ru(dppm)22(micro-dcbpy)] (PF6)2 (11) 168

7312 [Ru(dppm)22(micro-dcbpy)] (BPh4)2 (12) 169

7313 [ReCl(CO)3(micro-H2dcbpy)] (13) 169

7314 [Ru(CH=CHC6H4Me-4)(CO)(PPh3)22(micro-dcbpy)ReCl(CO)3] (14)

170

7315 [Ru(C(CequivCPh)=CHPh)(CO)(PPh3)22 (micro-[Re(dcbpy)(CO)3Cl])] (15)

170

7316 [Ru(dppm)22 (micro-[Re(dcbpy)(CO)3Cl])] (PF6)2 (16) 171

7317 (SC6H4CO2H-4)2 (17) 172

7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18) 172

7319 [AuSC6H4CO2Ru(dppm)22]PF6 (19) 173

7320 [(Ph3P)Au(SC6H4CO2-4)Ru(CH=CHC6H4Me-4)(CO)(PPh3)2] (20)

173

7321 [(Ph3P)Au(SC6H4CO2-4)Ru(C(CequivCPh)=CHPh)(CO)(PPh3)2] (21)

174

xv

7322 [(Ph3P)Au(SC6H4CO2-4)RuCH=CbpyReCl(CO)3((PPh3)2] (22) 175

7323 Au29[SC6H4CO2Ru(dppm)2]PF6 (NP1) 175


7225 Pd[SC6H4CO2Ru(dppm)2]PF6 (NP3) 176

74 Synthesis of complexes in Chapter 3

741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 178

742 [Pd(S2CNEt2)2] (24) 178

743 [(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25) 178

744 [(Ph3P)2PdS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2Pd(PPh3)2][PF6]2

(26) 179

745 [Pd(Me2dazdt)2]I6 (27) 180

746 [PdI2(Me2dazdt)] (28) 180

747 [Pd(Cy2DTO)2]I8 (29) 180

748 General set up for catalysis 181


751 (TBA)2[Pd2I6] (30) 186

752 Trans-PdI2(PPh3)2 (31) 186

753 [PdI2(dppe)] (32) 187

754 [PdI2(dppf)] (33) 187

755 General set up for catalysis reactions 187


761 (MeO)3SiCH2CH2CH2(Me)NCS2K (34) 192

762 (MeO)3SiCH2CH2CH22NCS2K (35) 192

763 [(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36) 193

764 [(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37) 193

xvi

765 Synthesis of silica nanoparticles (SiO2) 194

766 Synthesis of magnetic nanoparticles (Fe3O4 NP) 194

767 Synthesis of silica-coated iron oxide nanoparticles (SiO2Fe3O4 NP)

195

768 Immobilisation of complexes 36 and 37 on the SiO2 nanoparticles

195

769 Immobilisation of complexes 36 and 37 on the SiO2Fe3O4 nanoparticle

196


8 Appendices

A1 Crystal data and structure refinement for

[Ru(CH=CHC6H4Me-4)(S2C-N(CH2py)2)(CO)(PPh3)2] (5)

201


[Ru(dppm)22(micro-dcbpy)](BPh4)2 (12)

204


[(Ph3P)Au(SC6H4CO24)RuCH=CHbpyReCl(CO)3(CO)(PPh3)2]

(22)

208


[(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25-A)

212


[(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25-B)

216

A6 Crystal data and structure refinement for [(Ph3P)2PdS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2Pd(PPh3)2] [PF6]2 (26)

219


[(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36-A)

223


[(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36-B)

223

A9 Crystal data and structure refinement for [(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37)

229

B Calculation of palladium loading in 36SiO2Fe3O4 233

C Calculation of 3 mol of palladium loading 233

1



111 Why prepare multimetallic compounds

The inclusion of more than one metal centre within the same assembly might offer many

benefits especially if the properties of different metals are exploited A multimetallic

compound whether molecular or nanoscale in nature opens up new possibilities in a

variety of applications such as catalysis imaging and sensing1 Two popular

approaches in the construction of multimetallic assemblies containing large numbers of

metals are coordination polymers2 and metal-organic framework3 In these two cases

however most commonly multiple atoms of one single metal are linked

The preparation of multimetallic systems featuring two (or more) different metals is

considered to be a challenging task which often requires protectiondeprotection

strategies4 Otherwise specific donor combinations in the linkers can be tailored to be

selective for certain metals over others5 This can be best explained using Hard and

Soft acid-base (HSAB) theory In general lsquohardrsquo chemical species are small have a high

charge and are weakly polarizable while the reverse is the case for species termed

lsquosoftrsquo Essentially hard acids react preferentially (but not exclusively) to form stronger

bonds with hard bases and soft species tend to share a similar affinity for one another6

The differences in donor affinity have inspired much of the work in this thesis and led to

the exploration of the use of polyfunctional ligands containing a mixture of soft and hard

donor groups (oxygen nitrogen and sulfur) in the construction of multimetallic

assemblies Therefore it is appropriate that some background information is presented

on carboxylate dithiocarbamate and pyridine and ligands which are commonly used to

generate multimetallic systems

2

112 Dicarboxylates as linkers

Carboxylate groups have long been considered one of the most useful ligands in the

construction of metal complexes In a basic environment the parent carboxylic acid

will release a proton to form a carboxylate anion which is stabilised due to electron

delocalisation between the two electronegative oxygen atoms in the resonance

structure (Figure 111)7

Figure 111 Resonance structure of carboxylate anion

The versatile carboxylate anion (RCO2-) can then coordinate to metals in many

different ways whether in a monodentate mode or asymmetric and unsymmetric

chelates It can also act as a bridging bidentate ligand (syn-syn syn-anti or anti-anti)

(Figure 112)8

Figure 112 Binding modes of carboxylate anions8

Of the many carboxylate complexes known perhaps the most interesting ones have

four carboxylate ligands bridging two metal centres to form a lsquopaddle-wheel structurersquo

3

(Figure 113 A)8 This type of coordination allows the formation of a rigid lattice

structure and the presence of coordinative-unsaturation at the metal centres allow for

further reactivity including in catalysis Furthermore an impressive study by Whitwood

and co-workers has demonstrated a good catalytic activity in the addition of carboxylic

acids to propargyl alcohols to afford β-oxopropyl esters using ruthenium carboxylate

complex (Figure 113 B)9

Figure 113 A) Molecular structure of molybdenum acetate with lsquopaddle-wheelrsquo motif (Mo Blue O red C grey)8 B) cis-[Ru(κ2-O2CMe)2(PPh3)2] catalyst for the synthesis of β-oxopropyl esters9

113 Dithiocarbamates as linkers

In the history of the development of multimetallic complexes dithiocarbamates (DTCs)

have been widely employed as chelating agents as the sulfur lone pairs show a high

affinity towards metal centres in a range of oxidation states to form complexes

Debus10 reported the first examples of dithiocarbamic acids in the 1850s and there

has been substantial interest in DTC ligands over the intervening 160 years due to

their ability to stabilise both high and low oxidation states of different metals10 The

free DTC ligand is somewhat unstable in the acid form (dithiocarbamic acid) and so

DTCs are typically prepared as a salt by treating secondary amines with carbon

disulfide (CS2) in the presence of a strong base at room temperature in solvents such

as water methanol or ethanol This often leads to a quantitative yield of the DTC

product in its salt form (Equation 1)11

4

Equation 1 General equation for dithiocarbamate synthesis

The ability of DTC ligands to stabilise metals in various oxidation states can be

attributed to its two resonance forms The dithiocarbamate and thioureide forms can

stabilise low and high oxidation states respectively (Figure 114)11 If the

dithiocarbamate resonance form dominates the ligand will possess strong-field

characteristics while the thioureide form leads to more weak-field character The

degree to which each form contributes to the structure can be determined by

assessing the double bond character of the bond between the nitrogen and the carbon

in the S2C-N unit for example by X-ray crystallography This also leads to the

restricted rotation of this bond which is observed spectroscopically (eg NMR)11

Figure 114 DTC resonance forms

Delepine described the first example of a transition metal dithiocarbamate complex in

190712 Since this report a vast number of transition metal complexes (in all common

oxidation states) bearing a DTC ligand have been prepared1213 displaying a variety

of binding modes (Figure 115) The most common dithiocarbamate chelating

bidentate binding mode is A which is found with most transition metals This bidentate

coordination can be symmetrical A(1) or unsymmetrical A(2) the latter being known

as anisobidentate DTC ligands can also adopt a monodentate binding mode (B) with

the metal centre especially in the presence of sterically bulky co-ligands or when

linear coordination is favoured Monodentate dithiocarbamate coordination is quite

common in gold(I) chemistry for the latter reason14 The DTC can also bridge two

metals via mode C Complexes of gold in mono- or trivalent form commonly adopt

coordination mode C through the binding of the sulfur atom to a single metal centre15

5

Figure 115 Binding modes of DTC ligands

The potential for dithiocarbamates to be employed in metal-directed self-assembly has

been reviewed by Cookson and Beer13 Complex ring systems including

interpenetrating examples are accessible through the use of the versatile and easily

functionalised dithiocarbamate ligand (Figure 116)

Figure 116 Formation of dinuclear macrocyclic and macrocyclic complexes using dithiocarbamates13

The Wilton-Ely group has demonstrated that dithiocarbamate ligands can act as

excellent linkers to join transition metal units A significant finding was the stepwise

protocol for the synthesis of multimetallic complexes containing piperazine-based

dithiocarbamates as ligands This can be achieved by the isolation of a zwitterionic

dithiocarbamate species a molecule in which one end is activated (towards metals)

and the other (ammonium end) is protected Once the monometallic-dithiocarbamate

6

species is formed it can be used as a starting point for further transformations

Different types of transition metals can be added to the other end of the linker once

properly activated to form multimetallic species (Figure 117)1617

Figure 117 Piperazine-based dithiocarbamate complexes17


The combination of dicarboxylate and pyridine functional groups in a linker offers

excellent potential for the generation of heteromultimetallic systems Mixed-donor

ligands such as pyridine-4-carboxylic acid 4-(4-pyridyl)benzoic acid and 4-

cyanobenzoic acid18 have been reported as suitable linkers for the construction of

hetero-nuclear bi- tri- and pentametallic systems based on the individual donor

properties toward certain metals (Ru Rh Pd Pt Ag and Au) Figure 118 shows the

stepwise construction of heteromultimetallic assemblies comprising various transition

metals using this approach18

7

Figure 118 Stepwise construction of heteromultimetallic complexes using isonicotinic acid18

12 Gold nanoparticles and surface functionalisation

Michael Faraday first reported the well-defined synthesis of colloidal gold and made

the observation that a deep-red solution resulted from the reduction of aqueous

tetrachloroaurate (AuCl4macr) by phosphorus in carbon disulfide solvent19 However the

most reliable methods to synthesise well-defined gold nanoparticles (AuNPs) were

reported by Turkevich20 and Brust-Schiffrin21 The Turkevich method also known as

the ldquocitrate reduction methodrdquo employs sodium citrate as both reducing agent and

temporary capping agent20 The citrate shell can be displaced by adding thiol units

without changing the average size of the nanoparticles Nanoparticles in the size range

10 - 50 nm are typically formed and the size can be controlled through variation of

temperature and gold citrate ratio

Brust and Schiffrin reported a one-pot synthesis of AuNPs which produced an air

stable product with good control over the particle size (3 ndash 30 nm)21 Their original

approach employs tetraoctylammonium bromide (TOAB) as a phase-transfer reagent

to take aqueous AuCl4 into a toluene solution This is followed by the reduction of

AuCl4 by sodium borohydride in the presence of a thiol In general this two-phase

synthesis approach exploits the strong affinity of the thiol units for the gold surface to

enhance the stability of the nanoparticle (Figure 121)

8

Figure 121 Reduction of Au(III) to Au(0) proposed by Brust-Schiffrin21

Gold nanoparticles functionalised with transition metal units are receiving increasing

attention for their applications in nanotechnology particularly in catalysis and

sensing22 A pioneering work by Tremel and co-workers reported the surface

functionalization of gold nanoparticles with thiols bearing a ruthenium dimer which

successfully catalysed the ring-opening metathesis polymerisation of norbornene23 In

addition the surface functionalization of gold nanoparticles with a ferrocene units

through a modification of the Brust-Schiffrin method allows for the selective recognition

and binding of oxoanions which can then be sensed electrochemically24

However thiols (and thiolates) can be displaced from the AuNP surface through the

phenomenon known as stapling which consists of the gold atoms being lifted from the

surface allowing some of the surface units to be lost as a molecular gold-dithiolate

species2526 This issue has led to the search for a new generation of linkers capable

of tethering transition metal units to the gold surface without loss of product An

attractive alternative is the use of bifunctional dithiocarbamate ligands as their

interatomic S-S distances are close to ideal for epitaxial adsorption on the gold

surface Beer and co-workers showed that ruthenium or zinc units could be attached

to the surface of AuNPs using bipyridine or porphyrin chelates tethered to a

dithiocarbamate moiety These constructs have found application as anion

sensors2728 However the use of dithiocarbamate tethers to attach transition metals

is still not widespread with the majority of new examples being reported by the Wilton-

Ely group (Figure 122)1617

9

Figure 122 Gold nanoparticles functionalised with dithiocarbamate transition metal complexes1617


131 Homogeneous vs heterogeneous catalysis

The general definition of a catalyst is a substance that lowers the activation barrier of

a given reaction without being consumed during the transformation This property

leads to an increase in the rate of reaction allowing an excellent conversion in a short

time The most effective catalysts employed by industry in large-scale reactions to

produce organic compounds are based on transition metals29 The most famous

example is the utilisation of an iron catalyst in the Haber-Bosch process for ammonia

production which is critical for the fertiliser industry worldwide30 Conventionally

catalysis is divided into two different categories homogeneous and heterogeneous

catalysis

Homogeneous catalysis takes place when the catalyst and the reagents are in the

same phase This allows for better interaction leading to better activity A simple

modification of the nature of the ligand or the transition metal allows for tuning of the

steric and electronic properties generating better activity and selectivity31 In lab-scale

experiments the homogeneous catalyst is usually soluble in the solvent together with

the reactants providing the advantage of allowing the monitoring of the progression

of the reaction through spectroscopic methods such as infrared or nuclear magnetic

resonance (NMR) spectroscopy

10

However homogeneous catalysts experience a significant drawback in that the

catalyst recovery requires specific treatment processes to separate it from the

products Moreover the issue of stability under high temperatures and pressures is a

limitation for some catalytic reactions on an industrial scale32

In contrast heterogeneous catalysts are in a different phase to the reactants (usually

in solid form in contact with liquids or gases) Heterogeneous catalysts are used in

numerous industrial applications such as ammonia production30 and catalytic

cracking33 due to their exceptional properties easy recovery durability and high

catalytic activity34 Nevertheless one of the main limitations of heterogeneous

catalysis is associated with the low number of active species in respect to the mass

which affects the rate of reaction A possible solution is to maximise the interface

interaction between the phases by using nanoparticle sized catalysts which can

disperse in the reaction mixture like homogeneous catalysts34 The difference between

homogeneous and heterogeneous catalysis is summarised in Table 13135

Table 131 Comparison between homogeneous and heterogeneous catalysts

Property Homogeneous Heterogeneous

Phase Liquid Solid-GasLiquid

Characterisation Facile Difficult

Selectivity High Low

Separation Problematic Facile

Catalyst Recycling Expensive Simple

Mechanisms Easier to investigate Poorly understood

132 Oxidative functionalisation of C-H bonds

Carbon-hydrogen (C-H) bonds are covalent and exist in all organic molecules36 These

bonds allow a carbon atom to share its outer valence electrons with up to four

hydrogens Carbon-hydrogen bonds have a distinctive bond strength between 85 and

105 kcalmol and they are inert to homolytic and heterolytic cleavage37 Thus it

remains relatively challenging to transform an inert C-H bond into carbon-oxygen (C-

O) carbon-halogen (C-X) carbon-nitrogen (C-N) carbon-sulfur (C-S) or carbon-

carbon (C-C) bond

11

In 1955 Murahashi reported the first example of the C-H functionalization of 2-

phenylisoindolin-1-one in good yield from (E)-N-1-diphenylmethanimine catalysed by

cobalt complexes in the presence of carbon monoxide The ortho C-H bond in the

phenyl group is cleaved to form a new C-C bond in the reaction and afford the desired

product (Figure 131)38 These pioneering reports led to numerous later studies on C-

H cleavage catalysed by transition metals species39

Figure 131 Cobalt-catalysed C-H activation

Zeng and co-workers reported the use of pyridine N-oxide directing group for C-H

activation of acyclic systems as illustrated in Figure 132 (A) to form a product of 2-

(2-Benzyl-3-phenylpropanamido)pyridine-1-oxide40 An elegent contribution by Blakey

and co-workers described conditions for C-H functionalization of benzobisthiazole with

2-bromopyridine catalysed by palladium and copper complexes (Figure 132 B)41 A

versatile example of Cu-catalysed oxidation cycloalkane was demonstrated in the

conversion of benzaldehyde with cyclohexane to form intended product (Figure 132

C)42

Figure 132 Transition metal-catalysed C-H functionalization

12

1321 Mechanism and challenges

The chemistry of C-H functionalization has expanded rapidly since these discoveries

There are numerous theories regarding the mechanism of C-H functionalization

catalysed by transition metals The well-established mechanistic manifolds

popularised by Sanford are known as ldquoinner sphererdquo and ldquoouter sphererdquo

mechanisms37 The inner sphere mechanism (Figure 133) involves a two-step

reaction with (i) cleavage of the C-H bond to allow the formation of an organometallic

intermediate followed by (ii) insertion of the new functional group through

functionalization of an organometallic intermediate by reaction with either an external

reagent or at the metal centre37

Figure 133 Inner Sphere Mechanism

The critical feature of this mechanism is the formation of an organometallic

intermediate after the cleavage of the C-H bond either by oxidative addition or

electrophilic substitution (Figure 134) Transition metals such as Zr(II) Ru(0) and Ir(I)

are known to promote oxidative addition through direct insertion of the metal into a C-

H bond leading to an increase by two units of the oxidation state of the metal In

contrast the electrophilic substitution promoted by for example Pd(II) Pt(II) and

Rh(III) no change in oxidation state occurs because the covalently bound carbon

replaces a ligand43 The inner sphere mechanism is often favoured for reagents that

possess less sterically hindered C-H bonds through direct interaction with transition

metals

Figure 134 C-H bond cleavage mechanism

13

The essential feature of the outer sphere mechanism (Figure 135) is the formation of

a metal species with a high oxidation state comprising an activated ligand This is

followed by the cleavage of the C-H bond either by direct insertion or H-atom

abstractionradical rebound37 The feature that differentiates between outer-sphere

and inner-sphere mechanisms is that the substrate reacts directly with the activated

ligand (radical andor cationic species) instead of with the transition metal An

alternative terminology to lsquoinner spherersquo and lsquoouter spherersquo was introduced by

Crabtree44 who used lsquoorganometallicrsquo and lsquocoordinationrsquo respectively to describe the

mechanisms

Figure 135 Outer-sphere mechanism

The main challenge faced in developing a sustainable approach to C-H

functionalization is regioselectivity The criticality resides in the necessity to activate a

single C-H bond in molecules containing different carbon-hydrogen bonds Several

approaches have been used to address this problem including (i) the use of a

substrate containing directing groups such as nitrogen heterocycles amides oximes

ethers and imines45 (ii) the use of a substrate comprising weaker or activated C-H

bonds (benzylic or allylic systems)46 and (iii) the manipulation of the catalystligand to

control the selectivity47

1322 Palladium(II) complexes for C-H functionalization reactions

In the past few decades the palladium-catalysed C-H functionalization reaction has

become a vibrant and extremely active field of research4849 Traditionally palladium-

catalysed C-H functionalization proceeds via Pd0II catalytic cycles In contrast the

PdIIIV catalytic cycles are less investigated and the first example of this kind of

14

transformation was reported by Tremont and Rhaman50 in their work on methylation

of ortho C-H bonds in anilide (Figure 136) In this work a Pd(IV) intermediate was

proposed after reaction with methyl iodide (MeI) However a crystal of the Pd(IV)

intermediate was impossible to isolate from the reaction mixture

Figure 136 Methylation of ortho C-H bonds in anilide and proposed PdIV intermediate

Canty and co-workers51 reported the first crystal structure of a Pd(IV) intermediate to

prove the proposed oxidation of Pd(II) to Pd(IV) by MeI (Figure 137) A recent study

by Sanford describes the isolation of a Pd(IV) intermediate generated from the

acetoxylation of the complex which yielded a suitable crystal for X-ray studies52 This

evidence is crucial to support the PdIIPdIV redox chemistry

Figure 137 Structural evidence for PdIV intermediates

A number of examples of transformations based on PdII to PdIV catalytic cycles have

been described Sanford and co-workers reported the formation of a monophenylated

product (88) from the reaction of 2-phenyl-3-methyl pyridine with the iodine(III)

reagent [Ph2I]BF4 (Figure 138) This transformation employed a PdII to PdIV system

and can be considered as a practical and sustainable approach due to the inexpensive

ligand used as well as the absence of a strong base and the mild conditions

required53 The work of Daugulis and co-workers demonstrated another example of

15

arylation of a C-H bond using anilides as a substrate54 The reaction of substrates with

commercially available [Ph2I]PF6 yields a diphenylated product in a good yield

Figure 138 Arylation of C-H bond using PdII catalysts

More recent work by Sanford revealed a novel approach for oxidation and

halogenation of a non-activated C-H bond of benzo[h]quinoline via a PdIIPdIV catalytic

cycle (Figure 139) This substrate was chosen due to the presence of a nitrogen

directing group which allows the C-H functionalization to selectively occur at the C-10

position55 The catalytic reaction can be easily monitored by the integration of the 1H

NMR spectrum and affords the desired product with no by-products56 Furthermore

the reaction is a simple one-pot reaction which can be carried out without the exclusion

of air or water which is a significant advantage for applications in organic synthesis57

Figure 139 C-H Functionalization of benzo[h]quinoline

In a typical reaction benzo[h]quinoline is treated with PhI(OAc)2 (2 eq) and Pd(OAc)2

(2 mol) in acetonitrile to yield a mono-acetoxylated product By changing the solvent

to alcohols excellent yields of various alkyl-aryl ethers products [X = OMe OCH2CH3

OCH(CH3)2 and OCH2CF3] can be obtained Modification of the reaction conditions

16

using N-chloro- or N-bromosuccinimide (NCS or NBS) as oxidants instead of

PhI(OAc)2 leads to the formation of 10-chloro- or 10-bromo-benzo[h]quinoline57

A possible mechanism of reaction can be derived using the methoxylation of

benzo[h]quinoline (Figure 1310) as an example The proposed mechanism starts

with a C-H activation occurring specifically at C-10 to form a cyclopalladated

intermediate (PdII) followed by an oxidative addition step which leads to the formation

of a PdIV intermediate Finally reductive elimination allows for the release of the metal

and formation of a new C-OMe bond regenerating the PdII catalyst57

Figure 1310 Proposed mechanism of methoxylation of benzo[h]quinoline

It should be noted that previous work in the Wilton-Ely group demonstrated the ability

of palladium bearing imidazol(in)ium-2-dithiocarboxylate units to be effective pre-

catalysts in the methoxylation of benzo[h]quinoline using PhI(OAc)2 as an oxidant By

changing the oxidant to NCS 10-chlorobenzo[h]quinoline was formed in good yield

(80)56

133 Suzuki-Miyaura cross-coupling reaction

Transition metal catalysed cross-coupling reactions have long provided access to new

carbon-carbon bonds58 Various types of metal-catalysed carbon-carbon coupling

reactions have been reported such as those studied by Kumada-Corriu59 Negishi60

and Stille61 (Figure 1311) However the Suzuki cross-coupling reaction between an

organoboron compound (organoborane organoboronic acid organoboronate ester or

potassium trifluoroborate) and an aryl alkenyl or alkynyl halide catalysed by

palladium is one of the most widely used approaches for the formation of novel C-C

bonds Advantages of the reaction include mild reaction conditions low toxicity and

the stability offered by boron reagents compared to other coupling partners62

17

Figure 1311 General mechanism of metal catalysed cross-coupling reactions

Negishi and co-workers62 reported the first example of a Suzuki cross-coupling

reaction catalysed by palladium (Figure 1312) in 1978 The reaction of an alkynyl

borate with о-tolyl iodide catalysed by tetrakis(triphenylphosphine)palladium(0)

produced the desired product in good yield (92)

Figure 1312 First example of a Suzuki-Miyaura cross-coupling reaction

A year later Suzuki and co-workers reported a cross-coupling reaction between an

alkenyl boronate and an alkenyl bromide catalysed by Pd(PPh3)4 in the presence of a

base successfully generating the intended product (Figure 1313)63 Unlike other

organometallic reactions the presence of a base is essential for the Suzuki-Miyaura

reaction to proceed64

Figure 1313 Suzuki-Miyaura cross-coupling reaction

The general mechanism of the Suzuki-Miyaura cross-coupling reaction involves three

essential steps oxidative addition transmetallation and reductive elimination (Figure

1314)65 Oxidative addition of the aryl halide (Ar1X) is achieved from reaction with the

Pd(0) species to form the Pd(II) halide complex (Ar1PdXLn) Then a transmetallation

step occurs to convert Ar1PdXLn to the diaryl complex [(Ln)Pd(Ar1)(Ar2)] in the

18

presence of a base which participates in a cis-trans equilibrium The successive

reductive elimination step yields the biaryl product and re-generates the catalyst66

Figure 1314 General mechanism for the Suzuki-Miyaura cross-coupling reaction66

134 Immobilised transition metals on surfaces

There is enormous potential in combining the best properties of homogeneous and

heterogeneous catalysts into the same system However this remains a significant

challenge This goal can be achieved by immobilising the homogeneous catalyst onto

a solid support giving catalytic activity comparable to that of homogeneous catalysts

while offering the ease of separation of the catalyst from the products characteristic of

their heterogeneous counterparts67 Although a few studies in the early 1920s reported

the direct attachment of metals to various support materials68 a breakthrough came

with the early studies of Merrifield on the preparation of polymer-supported enzymes

for solid-phase peptide synthesis69 This finding was followed by the first example of

transition metal functionalised solid support (platinum complexes on sulfonated

polystyrene support)70

The immobilisation of transition metal complexes on solid supports can be

accomplished using appropriate organic linkers which covalently bond to the surface

19

of the solid support (Figure 1315) This method is expected to improve the interaction

between the heterogenised catalyst and reagent due to the pre-organisation of the

catalyst unit being towards the species in solution6771 Recent studies have moved

beyond polymeric supports to cheaper alternatives such as silica and zeolites

Figure 1315 Immobilisation of homogeneous catalysts on a solid support

This immobilisation approach offers ready separation of catalyst from the products

For example insoluble support (polymers silica and zeolites) can be separated by

filtration processes whereas liquid-liquid extraction can be used to recover soluble

support (polymers) In order to increase the effectiveness of the recovery process a

more reliable technique employing magnetic nanoparticles as supports has also been

explored This approach offers the possibility for a lab scale reaction to use a hand-

held magnet to separate the catalyst from the reaction mixture72 In the following

sections some background information will be provided on iron-oxide silica and iron-

oxide silica coated nanoparticles

1341 Iron oxide nanoparticles

Magnetic nanoparticles (MNPs) can be derived from many different precursors such

as metals alloys iron oxides and ferrites by several well-established procedures such

as co-precipitation73 sol-gel techniques74 hydrothermal reactions75 and microwave

irradiation76 Among all the MNPs available iron oxide (Fe3O4) or magnetite

nanoparticles are considered the best option as supports in catalysis because of the

inexpensive starting materials and straightforward synthetic protocols77 The co-

precipitation method is known to be a simple and effective way to synthesis Fe3O4

NPs Monodispersed iron oxide nanoparticles are obtained by treatment of an

aqueous solution of Fe2+Fe3+ with a base in an inert environment at ambient or

elevated temperatures78 The quality of the Fe3O4 nanoparticles obtained is

reproducible after optimisation of several parameters such as temperature solvent

20

and Fe2+Fe3+ ratio78 The general equation for the formation of Fe3O4 nanoparticles is

presented in Equation 2

Equation 2 General mechanism of iron oxide nanoparticles

The unfunctionalised nanoparticles formed are prone to oxidation upon exposure to

air and quickly aggregate due to the small interparticle distance high surface area and

strong van der Waals forces This problem can be solved by applying an organic

coating such as long chain fatty acids or alkylamines to the surface of the

nanoparticles to promote passivation of iron oxide and form a highly uniform and

monodispersed product79 Another interesting approach is the use of an inorganic

material such as silica to stabilise and create a coating shell covering the magnetic

nanoparticles This technique offers several advantages over organic coating 1) it

avoids leaching problems of the Fe3O4 core during severe shaking or mixing reaction

conditions and 2) the presence of Si-OH moieties on the surface opens up the

possibility to functionalise the nanoparticles72

1342 Silica nanoparticles

The preparation of silica nanoparticle relies on the hydrolysis and condensation of the

silica source The best known and most widely-used procedure to prepare silica

nanoparticles was developed by Stoumlber and co-workers80 An ethanolic solution of

tetraethylorthosilicate (TEOS) is treated with water in the presence of a base

(ammonia solution) as a catalyst to form a white precipitate of silica nanoparticles81

The first step is the hydrolysis initiated by the attack of hydroxyl anions on TEOS

promoted by the ammonia (an ethoxy group of TEOS being substituted by a hydroxyl

group) The process is followed by a condensation reaction (alcohol or water

condensation) to form Si-O-Si bonds (Figure 1316)82

Figure 1316 General mechanism of silica nanoparticle preparation

21

1343 Iron oxides silica-coated nanoparticles (Fe3O4SiO2)

A few methods for synthesising Fe3O4SiO2 are available in the literature such as

sol-gel 83 and microemulsion approaches84 An early report by Ying and co-workers85

demonstrated the effectiveness of silica coated iron-oxide nanocomposites as

magnetic catalyst supports These findings were considered a turning point for the

development of various catalyst systems based on silica-coated iron oxide

nanoparticles The attachment of metal complex catalysts to the surface of

Fe3O4SiO2 can be achieved in two different ways (1) direct reaction of a metal

complex with Fe3O4SiO2 nanoparticles (2) coordination of the metal complex

precursor to Fe3O4SiO2 nanoparticles equipped with a chelating surface unit72

Figure 1317 shows the formation of Fe3O4SiO2 nanoparticles with a β-oxoiminato-

phosphanyl palladium complex attached to the surface through the direct reaction of

the metal complex with the magnetic nanoparticles (Figure 1317 A) This approach

is achieved through condensation of an Si(OEt)3 moiety in the complex with the Si-OH

binding site on the surface of the silica shells86 Alternatively Fe3O4SiO2 modified

with di(2-pyridyl) units were formed by the reaction of acetylene-terminated di(2-

pyridyl) and azide functionalised Fe3O4SiO2 This chelating ligand modified

Fe3O4SiO2 nanoparticle was then treated with [PdCl2(NCMe)2] to yield a magnetic

nanoparticle bearing palladium surface units (Figure 1317 B)

22

Figure 1317 Different approaches to functionalise Fe3O4SiO2 with palladium complexes

135 Catalysis by immobilised Pd(II) complexes

Over the years there have been several attempts to immobilise Pd(II) catalysts on a

range of different supports8788 This literature review will focus mainly on the

immobilisation of Pd(II) catalysts on magnetic nanoparticles due to the facile

separation properties displayed89

Gao and co-workers successfully employed silane groups to functionalize Pd-NHC

complexes onto the surface of maghemite (Fe2O3) nanoparticles (Figure 1318)90

This indirect approach is possible due to the high affinity of silane groups for the

uncoordinated surface of Fe2O3 nanoparticles91 This recoverable magnetic catalyst

was employed in Suzuki coupling reactions showing excellent catalytic activity for aryl

halide substrates Recycling experiments were conducted by separation of the

magnetic catalyst using an external magnet showing no loss in catalytic activity90

23

Figure 1318 Functionalization of Pd-NHC complexes on the surface of Fe2O3 nanoparticles

In another contribution Gao and co-workers introduced a novel iron oxide

nanostructure coated with a thin layer of polymer (lightly cross-linked polymers of

styrene and 14-vinylbenzene chloride) This combination of polymers prevents

aggregation of the iron oxide nanoparticles and provides good support for catalyst

functionalization The immobilisation of the catalyst was achieved by treating the

nanoparticles with 1-methylimidazole (Figure 1319) The functionalization approach

was successfully carried out by employing Na2CO3 to deprotonate the imidazolium

group to form an N-heterocyclic carbene (NHC) which can then form robust complexes

with Pd(OAc)292 This magnetic catalyst system was tested for activity in the Suzuki

cross-coupling reaction of aryl halides and aryl boronic acid giving a quantitative yield

of product92

Figure 1319 Functionalization of Pd-NHC complexes on the surface of polymer coated Fe2O3 nanoparticles

There are relatively few examples of immobilised palladium catalysts on the surface

of silica-coated nanoparticles (Figure 1320) Jin and co-workers reported a system

based on Fe3O4SiO2 with β-oxoiminato-phosphanyl-palladium surface units which

proved to be an active catalyst for Suzuki Sonogashira and Stille reactions86 This

magnetically recoverable Pd(II) catalyst demonstrated a high conversion to the desired

24

product (71 - 94) in Suzuki cross-coupling reactions with a diverse range of aryl

chloride and aryl boronic acid substrates The Sonogashira coupling of aryl chlorides

with alkynes and the Stille coupling of aryl chlorides with organostannanes employing

the same catalyst produced more than 70 conversion to products from different

types of substrates86

Gao et al explored a novel synthetic method to attach di(2-pyridyl)methanol-derived

palladium chloride to the surface of Fe3O4SiO2 which showed high catalytic activity

in Suzuki coupling of a variety of aryl bromoarene substrates93 The re-use of this

magnetic catalyst for the reaction of 4-bromoacetophenone with phenylboronic acid

showed only 5 loss in catalytic activity after five subsequent reactions Thiel and co-

workers designed a new system of Fe3O4SiO2 nanoparticles functionalised with

palladium(II) phosphine complexes which serve as excellent catalysts for the Suzuki-

Miyaura coupling of phenyl bromide and phenylboronic acid (99 conversion) using

Cs2CO3 and dioxane as base and solvent respectively94

Figure 1320 Functionalisation of palladium complexes on the surface of silica-coated Fe3O4 nanoparticles

25

14 Recovery and re-use of palladium

141 Palladium supply and demand

The platinum group metals (PGMs) are six noble and valuable transition metallic

elements in the d-block of the periodic table ruthenium (Ru) osmium (Os) rhodium

(Rh) iridium (Ir) palladium (Pd) and platinum (Pt)95 The PGMs are classified as

ldquocritical raw materialsrdquo due to their rarity on earth in conjunction with their high

economic importance96 Palladium is considered to have a particularly high demand

due to its exclusive chemical and physical97 properties that lead to various industrial

applications (catalytic converters dentistry ceramic capacitors)

Palladium is known to have low abundance (only 0005 ppm per tonne of earth crust)98

and is mined only in certain places around the world dominated by sources in Russia

(43) South Africa (30) Canada (10) and the United States (6) which together

produce 90 of the global palladium supply99 Therefore geopolitics plays a factor in

the production of palladium100 potentially affecting the supply and price as it did in

2000 In this year the prices of palladium reached 1100 USDOz and even surpassed

the value of platinum briefly due to Russia delaying exports at the same time as the

substitution of platinum with palladium in three-way catalytic converters (TWCs)

became more widespread101 Its price remained fairly high in these few years nearly

always above 500 USDOz 4-5 times greater than the much more stable price in the

1990s of approximately 100 USDOz (Figure 141)

Figure 141 Palladium and platinum price in US Dollar per ounce between 1992 and 2016102

0

500

1000

1500

2000

2500

1992 1997 2003 2008 2014

Pri

ce (

USD

pe

r O

z)

Year

Pt

Pd

26

Moreover palladium has a significant market demand dominated by manufacturing

of TWCs in the automotive industry (approximately 82 of the total production)99 due

to the stringent emissions legislation implemented in the United States (US) that

required all vehicles produced after 1975 to be equipped with a catalytic converter

Incomplete combustion of gasoline and diesel in vehicles produces carbon monoxide

(CO) unburned hydrocarbons (HC) nitrogen oxides (NO) and particulate matter The

installation of the three-way catalytic converter (TWCs) in the vehicle exhaust pathway

transforms most of these harmful gases into less toxic substances (nitrogen carbon

dioxide and water)103

It was predicted that a number of vehicles on the roads worldwide would grow close

to 1300 million by 2030104 This scenario led to double the demand for palladium

between 2003 to 2013 (Figure 142) This increasing trend of palladium demand

reached the highest point around 2009 due to the boost in automobile production in

developing countries such as China and India105 The demand for palladium has

increased over the years but supply has been falling since 2007 and did not display

any sign of improvement106 Even taking recycling into account there has been a net

decrease in stocks in recent years Thus there are strong drivers and incentives both

environmentally and economically for obtaining palladium and its compounds from

alternative sources such as recycling and finding innovative ways of deploying them

Figure 142 Palladium supply and demand from 2000 to 2013106

27

142 Recovery methods from secondary sources of palladium

The recovery and recycling of used palladium from spent TWCs provide a growing

secondary source of PGMs to support the market demand107 The short lifespan (8-10

years) of catalytic converters due to fouling poisoning thermal degradation and

sintering could become a major environmental problem if they were to be disposed of

directly into landfills108 Generally catalytic converters contain honeycomb structured

ceramic monolith support a washcoat (Al2O3) with the addition of CeO2 and ZrO2 in

more recent designs109 to maximise surface area and highly dispersed quantities of

Pd Pt and Rh with exact compositions varying among producers Typical loading of

palladium is 05 - 30 by weight109 The low and well-dispersed metal loading along

with the complicated composition due to sintering phenomena occurring during the

lifespan of the complex ceramic matrix material present obvious difficulties in

recycling the precious metals from catalytic converters Thus the large amount of

palladium and other precious metals present in catalytic converters require a method

of recovery as they meet the end of their lifetime which will allow them to be recycled

into new and useful materials110

Three main ways of recovering metals from waste have been explored and developed

and these are known as a pyrometallurgical biometallurgical and hydrometallurgical

process111 each coming with its own advantages and disadvantages The most well-

established and widely used approach in industry is the pyrometallurgical one

developed and popularised by the company Johnson Matthey This technique requires

a high operating temperature (1500 - 1700 degC) to generate a molten metal crucible

used to treat milled catalytic converter material The process leads to the formation of

molten slag which is allowed to settle in order to collect PGMs The main limitation of

the pyrometallurgical process is its high energy demand and the lack of selectivity

towards palladium requiring further chemical separation to extract the different

PGMs112

An alternative is presented by the hydrometallurgical method due to its lower energy

demands and its environmental impact in respect to smelting This process requires

the metal to be dissolved in an aqueous solution containing a strong oxidising agent

and cyanide to leach the precious metals from the feedstocks under mild

conditions113 The hydrometallurgy technique offers easier control better selectivity

28

and predictability in the extraction of precious metals but the presence of harmful

reagents in the commercial process raises significant safety and environmental

concerns114

The biometallurgical method is another option to recover the precious metals by

employing a bacteria-assisted reaction115 (bioleaching process) or physio-chemical

and independent metabolism process to remove precious metal from a solution of

biological materials (biosorption process)116 This technique is environmentally

friendly However it has been reported only on a lab scale and has been limited to

only a few metals so far117

Recent literature from our collaborators at the University of Cagliari Italy reported the

possibility of extracting palladium selectively from mixtures containing rhodium and

platinum in well-milled TWC waste This approach employs a relatively sustainable

sulfur chelating organic ligand halogen adduct NN-dimethylperhydrodiazepine-23-

dithione diiodine to recover palladium from TWCs under mild aerobic conditions (80

degC) in a one-pot reaction to form a palladium(II) complex in 90 yield118 A further

energy-intensive process (chemical or electrochemical reduction) step is still required

to convert the complex into palladium powder form suitable for re-use making the

whole process less practical for palladium recycling Far better would be to use the

palladium complexes produced by this approach directly as a homogeneous catalyst

The patented process to recover palladium metals form TWCs is summarised in Figure

143

29

Figure 143 Patented palladium recovery process119

15 Thesis overview

The work presented in this thesis focuses primarily on the synthesis and

characterisation of multimetallic compounds and surface functionalization of

nanoparticles for applications in catalysis

Chapter 1 comprises all the relevant literature for multimetallic compounds

nanoparticle surface functionalization catalysis and recovery

Chapter 2 provides a stepwise protocol for the construction of a multimetallic assembly

using polyfunctional ligands (dipicolylamine 22rsquo-bipyridine-44rsquo-dicarboxylic acid and

4-mercaptobenzoic acid) comprising nitrogen dithiocarboxylate and dithiocarbamate

chelating moieties Surface functionalization of gold and palladium nanoparticles is

also investigated

Chapter 3 outlines the preparation of dithiocarbamate and dithiooxamide palladium

complexes as potential catalysts for C-H functionalization reactions

30

Chapter 4 describes the employment of iodine and a tetrabutylammonium salt [TBA]I

to dissolve the palladium metal in spent TWCs and precipitate it as (TBA)2[Pd2I6] This

complex is used as a homogeneous catalyst for C-H functionalization and Suzuki-

Miyaura cross-coupling reactions

Chapter 5 explains the development of novel Pd-catalysts bearing two different silyl

amines and their functionalisation on the surface of silica-coated iron-oxide

nanoparticles The catalytic performance of homogeneous (molecular) and

heterogeneous (supported) catalysts in C-H functionalization is examined

Chapter 6 (Conclusion) summarises the whole thesis

Chapter 7 provides the experimental procedures in detail

31

16 References

1 C Amijs G van Klink and G van Koten Dalton Trans 2005 308ndash327

2 C Janiak Dalton Trans 2003 14 2781ndash2804

3 C Janiak and J K Vieth New J Chem 2010 34 2366ndash2388

4 S Sung H Holmes L Wainwright A Toscani G J Stasiuk A J P White J D Bell and J D E T Wilton-Ely Inorg Chem 2014 53 1989ndash2005

5 J D E T Wilton-Ely D Solanki and G Hogarth Eur J Inorg Chem 2005 2 4027ndash4030

6 B G Ralph Pearson J Am Chem Soc 1963 85 3533ndash3539

7 P Bruice Organic Chemistry Prentice Hall 2006

8 G B Deacon and R J Phillips Coord Chem Rev 1980 33 227ndash250

9 N P Hiett J M Lynam C E Welby and A C Whitwood J Organomet Chem 2011 696 378ndash387

10 H Debus Justus Liebigrsquos Ann Chem 1850 73 26

11 G Hogarth Transition Metal Dithiocarbamates 1978-2003 Wiley-Blackwell 2005

12 M Delepine Bull Soc Chim Fr 1907 144 1125ndash1127

13 J Cookson and P D Beer Dalton Trans 2007 1459

14 Eduardo J Fernaacutendez Joseacute M Loacutepez-de-Luzuriaga A Miguel Monge E Olmos M C G And A Laguna and P G Jones Inorg Chem 1998 37 5532ndash5536

15 E J Fernaacutendez J M Loacutepez-de-Luzuriaga M Monge E Olmos A Laguna M D Villacampa and P G Jones J Clust Sci 2000 11 153ndash167

16 E R Knight A R Cowley G Hogarth and J D E T Wilton-Ely Dalton Trans 2009 607ndash609

17 E Knight N Leung Y Lin and A Cowley Dalton Trans 2009 3688ndash3697

18 S Naeem A Ribes A J P White M N Haque K B Holt and J D E T Wilton-Ely Inorg Chem 2013 52 4700ndash4713

19 M Faraday Phil Trans R Soc L 1857 147 145ndash181

20 J Turkevich P C Stevenson and J Hillier Discuss Faraday Soc 1951 11 55ndash75

21 M Brust M Walker D Bethell D J Schiffrin and R Whyman J Chem Soc 1994 7 801ndash802

22 E K Beloglazkina A G Majouga R B Romashkina N V Zyk and N S Zefirov Russ Chem Rev 2012 81 65ndash90

23 M Bartz J Kuumlther R Seshadri and W Tremel Angew Chemie Int Ed 1998

32

37 2466ndash2468

24 A Labande J Ruiz and D Astruc J Am Chem Soc 2002 124 1782ndash1789

25 Y Zhao W Peacuterez-Segarra Q Shi and A Wei J Am Chem Soc 2005 127 7328ndash7329

26 J B Schlenoff M Li and H Ly J Am Chem Soc 1995 117 12528ndash12536

27 P D Beer D P Cormode and J J Davis Chem Commun 2004 414ndash415

28 M S Vickers J Cookson P D Beer P T Bishop and B Thiebaut J Mater Chem 2006 16 209ndash215

29 G P Chiusoli and P M Maitlis Metal-catalysis in industrial organic processes RSC Publishing 2008

30 M Appl in Ullmannrsquos Encyclopedia of Industrial Chemistry Wiley-VCH Verlag GmbH amp Co KGaA Weinheim Germany 2011

31 V Polshettiwar R Luque A Fihri H Zhu M Bouhrara and J-M Basset Chem Rev 2011 111 3036ndash3075

32 B Cornils and W A Herrmann J Catal 2003 216 23ndash31

33 United States Pat 1984

34 G Bond P Atkins J Holker and A Holliday Heterogeneous Catalysis Principles and Applications Clarendon 1987

35 G Ertl Handbook of heterogeneous catalysis Wiley-VCH 2008

36 M D Smith and J March Marchrsquos Advanced Organic Chemistry Reactions Mechanisms and Structure 6th ed 2007 vol 11

37 A R Dick and M S Sanford Tetrahedron 2006 62 2439ndash2463

38 S Murahashi J Am Chem Soc 1955 77 6403ndash6404

39 Y Guari S Sabo-Etienne and B Chaudret Eur J Inorg Chem 1999 1999 1047ndash1055

40 J Liu Y Xie W Zeng D Lin Y Deng and X Lu J Org Chem 2015 80 4618ndash4626

41 J L Bon D Feng S R Marder and S B Blakey J Org Chem 2014 79 7766ndash7771

42 J Zhao H Fang J Han and Y Pan Org Lett 2014 16 2530ndash2533

43 J A Labinger and J E Bercaw Nature 2002 417 507ndash514

44 R H Crabtree J Chem Soc Dalt Trans 2001 0 2437ndash2450

45 T W Lyons and M S Sanford Chem Rev 2010 110 1147ndash1169

46 C Guo J Song S-W Luo and L-Z Gong Angew Chemie Int Ed 2010 49 5558ndash5562

47 Y-H Zhang B-F Shi and J-Q Yu J Am Chem Soc 2009 131 5072ndash5074

33

48 A D Ryabov Chem Rev 1990 90 403ndash424

49 H M L Davies and D Morton J Org Chem 2016 81 343ndash350

50 S J Tremont and H U Rahman J Am Chem Soc 1984 106 5759ndash5760

51 P K Byers A J Canty B W Skelton and A H White J Chem Soc Chem Commun 1986 0 1722ndash1724

52 R D Allison W K Jeff and M S Sanford J Am Chem Soc 2005 127 12790ndash12791

53 K Dipannita R D Nicholas L V Desai and M S Sanford J Am Chem Soc 2005 127 7330ndash7331

54 O Daugulis and V G Zaitsev Angew Chemie Int Ed 2005 44 4046ndash4048

55 G E Hartwell R V Lawrence and M J Smas J Chem Soc D 1970 912

56 M J D Champion R Solanki L Delaude A J P White and J D E T Wilton-Ely Dalton Trans 2012 41 12386ndash12394

57 A R Dick K L Hull and M S Sanford J Am Chem Soc 2004 126 2300ndash2301

58 E de Meijere A Diedrich F Metal-Catalyzed Cross-Coupling Reactions Wiley-VCH Weinheim 2nd edn 2004

59 M Kumada Pure Appl Chem 1980 52 669

60 E Negishi Q Hu Z Huang M Qian and G Wang Aldrichim Acta 2005 38 71ndash87

61 J Stille Angew Chem 1986 98 504ndash519

62 C-J Li Chem Rev 2005 105 3095ndash3166

63 N Miyaura K Yamada and A Suzuki Tetrahedron Lett 1979 20 3437ndash3440

64 N Miyaura and A Suzuki J Chem Soc Chem Commun 1979 10 866ndash867

65 N Miyaura and T Yanagi Synth Commun 1981 11 513ndash519

66 A J J Lennox and G C Lloyd-Jones Chem Soc Rev 2014 43 412ndash443

67 A M Catherine J D Mark and M Bradley Chem Rev 2002 102 3275ndash3300

68 T Sabalitschka and W Moses Berichte der Dtsch Chem Gesellschaft (A B Ser 1927 60 786ndash804

69 R B Merrifield Sci Total Environ 1965 150 178ndash185

70 Chem Abs 1969 71 114951

71 N E Leadbeater and M Marco Chem Rev 2002 102 3217ndash3274

72 D Wang and D Astruc Chem Rev 2014 114 6949ndash6985

73 L C Brian V L Kolesnichenko and C J OrsquoConnor ChemRev 2004 104 3893ndash3946

34

74 J D Mackenzie and E P Bescher Acc Chem Res 2007 40 810ndash818

75 K Byrappa and T Adschiri Prog Cryst Growth Charact Mater 2007 53 117ndash166

76 I Bilecka and M Niederberger Nanoscale 2010 2 1358

77 M B Gawande P S Branco and R S Varma Chem Soc Rev 2013 42 3371

78 A-H Lu E L Salabas and F Schuumlth AngewChemIntEd 2007 46 1222ndash1244

79 A L Willis J T Nicholas and S OrsquoBrien ChemMater 2005 17 5970ndash5975

80 W Stober A Fink and A E Bohn J Colloid Interface Sci 1968 26 62ndash69

81 C J Brinker and G W Scherer Sol-gel science  the physics and chemistry of sol-gel processing Academic Press 1990

82 I A M Ibrahim A A F Zikry M A Sharaf and A Zikry J Am Sci 2010 6 985ndash989

83 G Ennas A Musinu G Piccaluga D Zedda D Gatteschi C Sangregorio J L Stanger G C And and G Spano ChemMater 1998 10 495ndash502

84 S Swadeshmukul R Tapec N Theodoropoulou J Dobson A Hebard and T Weihong Langmuir 2001 17 2900ndash2906

85 K Y Dong S L Su and J Y Ying Chem Mater 2006 18 2459ndash2461

86 M J Jin and D H Lee Angew Chemie - Int Ed 2010 49 1119ndash1122

87 A Molnar Chem Rev 2011 111 2251ndash2320

88 L Yin and J Liebscher Chem Rev 2006 107 133ndash173

89 R B N Baig and R S Varma Chem Commun 2013 49 752ndash770

90 Z Yan D S Philip and Y Gao JOrgChem 2005 71 537ndash542

91 T Rajh L X Chen K Lukas T Liu M C Thurnauer and D M Tiede JPhyChemB 2002 106 10543ndash10552

92 P D Stevens J Fan H M R Gardimalla A Max Yen and Y Gao Org Lett 2005 7 2085ndash2088

93 G Lv W Mai R Jin and L Gao Synlett 2008 2008 1418ndash1422

94 S Shylesh L Wang and W R Thiel Adv Synth Catal 2010 352 425ndash432

95 H Renner G Schlamp I Kleinwaumlchter E Drost H M Luumlschow P Tews P Panster M Diehl J Lang T Kreuzer A Knoumldler K A Starz K Dermann J Rothaut R Drieselmann C Peter and R Schiele in Ullmannrsquos Encyclopedia of Industrial Chemistry Wiley-VCH Verlag GmbH amp Co KGaA Weinheim Germany 2001

96 Critical raw materials for the EU Report of the Ad-hoc Working Group on defining critical raw materials - European Commission 2010

35

97 David R Lide CRC Handbook of Chemistry and Physics 2000

98 Report on critical raw materials for the EU 2014

99 J Matthey PGM Market Report Forecat of Platinium Supply and Demand in 2016 2016

100 A J Hunt Element recovery and sustainability Royal Society of Chemistry 2013

101 H Christian Metall 2006 60 30ndash42

102 National Minerals Information Center United States Geological Survey Mineral Com- modity Summaries 2017 httpsmineralsusgsgovmineralspubscommodity platinummcs-2017-platipdf (visited on 072017) (accessed 22 February 2018)

103 J Kašpar P Fornasiero and N Hickey Catal Today 2003 77 419ndash449

104 M N Rao and H V N Rao Air pollution Tata McGraw-Hill 1989

105 A Helmi F Gallucci and M van Sint Annaland Int J Hydrogen Energy 2014 39 10498ndash10506

106 Market data tables httpwwwplatinummattheycomservicesmarket-researchmarket-data-tables (accessed 23 February 2018)

107 H E Hilliard PlatiniumndashGroup Metals 2003

108 B H Robinson Sci Total Environ 2009 408 183ndash191

109 M Cuscusa A Rigoldi F Artizzu R Cammi P Fornasiero P Deplano L Marchiograve and A Serpe ACS Sustain Chem Eng 2017 5 4359ndash4370

110 V Gombac T Montini A Falqui D Loche M Prato A Genovese M L Mercuri A Serpe P Fornasiero and P Deplano Green Chem 2016 18 2745ndash2752

111 J Cui and L Zhang J Hazard Mater 2008 158 228ndash256

112 M Benson C Bennett J Harry M Patel and M Cross Elsevier 2000 31 1ndash7

113 D Andrews A Raychaudhuri and C Frias J Power Sources 2000 88 124ndash129

114 C A Nogueira A P Paiva P C Oliveira M C Costa and A M R da Costa J Hazard Mater 2014 278 82ndash90

115 J Wang J Bai J Xu and B Liang J Hazard Mater 2009 172 1100ndash1105

116 G M Gadd J Chem Technol Biotechnol 2009 84 13ndash28

117 L Zhang and Z Xu J Clean Prod 2016 127 19ndash36

118 A Serpe F Bigoli M C Cabras P Fornasiero M Graziani M L Mercuri T Montini L Pilia E F Trogu and P Deplano Chem Commun 2005 8 1040ndash1042

36

119 K A Jantan C Y Kwok K W Chan L Marchio A J P White P Deplano A Serpe and J D E T Wilton-Ely Green Chem 2017 19 5846ndash5853

37

2 Stepwise construction of multimetallic assemblies and

nanoparticle surface functionalisation

21 Background and significance

In the last decades significant efforts have been made to explore the incorporation of

more than one transition metal unit within the same covalent network The ability to do

so offers the possibility of exploring multiple applications in many areas such as

catalysis1 sensing2 and imaging3 especially if the properties of different metals can

be exploited However the synthesis of multimetallic complexes consisting of two

different metals has proved to be a challenging task This difficulty can be overcome

by employing a protectiondeprotection system of the donor groups or by carefully

tailoring the donor groups of the organic linker to specific metal centres Another

attractive and straightforward method is to tailor bifunctional linkers to the transition

metals involved This approach has been used by us4 and others5 to generate

multimetallic complexes comprising different transition metals

Previous study in the group67 have mainly focused on sulfur and carboxylate ligands

based on the 11rsquo-dithio compounds which have proven to be suitable for the stepwise

construction of multimetallic assemblies and nanoparticle surface functionalization In

this chapter the focus is to employ a mixed donor ligand to generate multimetallic

complexes This ligand contains at least two different donor groups which possess an

affinity towards particular metals which is a more reliable strategy than

protectiondeprotection routes With this intention the reactivity of three different

simple and commercially available organic ligands comprising different donor groups

(oxygen nitrogen and sulfur) will be explored The chosen compounds are

dipicolylamine 22-bipyridine-44-dicarboxylic acid and 4-mercaptobenzoic acid

(Figure 211)

Figure 211 Ligands used to generate multimetallic complexes

38

Kabzinska and co-workers first synthesised the dipicolylamine ligand8 Most of the

work involving this ligand centred on the strong affinity of the three nitrogen donors to

bind zinc atoms allowing applications as chemosensors and imaging agents to be

explored9 In the present work dipicolylamine was converted to the corresponding

dithiocarbamate ligand which allows different reactivity to be displayed at sulfur and

nitrogen donors in the preparation of multimetallic assemblies

Commercially available dicarboxylic acid and bipyridine compounds have attracted

attention as a bridging ligand particularly in coordination polymers10 and metal-organic

frameworks (MOFs)11 due to the presence of nitrogen and carboxylate donors which

form stable coordination complexes with metals in a range of oxidation states Dye-

sensitized solar cell applications have used photosensitizers based on Ru(II)12 and

Ir(III) complexes13 and this has motivated recent interest in the 22-bipyridine-44-

dicarboxylic acid ligand as a bidentate N-donor ligand However the work described

here will exploit all three available donor units for the construction of

heteromultimetallic complexes based on rhenium and group 8 metals in a controllable

manner

The research was also extended to explore the use of thiols as donors in the

bifunctional linker 4-mercaptobenzoic acid The different reactivity of sulfur and oxygen

allows both thiolate and disulfide forms of 4-mercaptobenzoic acid to be used to

generate heteromultimetallic complexes based on gold and group 8 metals as well as

surface functionalization of gold and palladium nanoparticles

Some of the results in this chapter have been published in an Inorganic Chemistry

paper entitled lsquoBifunctional Chalcogen Linkers for the Stepwise Generation of

Multimetallic Assemblies and Functionalized Nanoparticlesrsquo14

211 Aims and objective

This chapter aims to employ a differently mixed donor ligand to synthesise a mono bi

tri and multimetallic complexes It was followed by surface functionalization of gold

and palladium nanoparticles using Ru complexes bearing disulfide linker

39

22 Monometallic complexes bearing dithiocarbamate ligands

Secondary amines have been extensively used to prepare dithiocarbamate (DTC)

ligands which exhibit excellent stability and offer fascinating electrochemical and

optical properties15 In this section the tridentate ligand dipicolylamine (a secondary

amine with two picolyl substituents) was used as a precursor to prepare a DTC ligand

which was later used to generate metallic assemblies

The yellow liquid dipicolylamine is commercially available and can easily be prepared

by reductive amination of 2-picolylamine and 2-pyridinecarboxaldehyde in good yield

and sufficient purity (1H NMR IR spectroscopic and MS analysis) so as not to require

any additional purification16 The diagnostic resonance of the methylene protons

(NCH2Py) appeared as a singlet at 393 ppm and other proton resonances were

observed in the aromatic region of the 1H NMR spectrum The infrared spectroscopic

analysis displayed absorptions assigned to the N-H stretch at 3296 cm-1 along with a

band at 1433 cm-1 attributed to the C-N stretch The overall structure of dipicolylamine

was confirmed by a molecular ion in the electrospray mass spectrum (+ve mode) at

mz 200

Figure 221 Dithiocarbamate salt generated from dipicolylamine

Dipicolylamine was converted to the dithiocarbamate salt KS2CN(CH2py)2 (1) in good

yield (84) by deprotonation of the secondary amine with potassium carbonate in the

presence of carbon disulfide (Figure 221) The presence of the CS2 unit was

confirmed by the typically downfield resonance at 216 ppm in the 13C1H NMR

spectrum The protons of the methylene arm (NCH2Py) gave rise to a resonance in

the 1H NMR spectrum at a different chemical shift (559 ppm) compared to the same

feature in the precursor (393 ppm) Four proton resonances belonging to pyridine

were observed at 704 (py-H5) 730 (py-H3) 753 (py-H6) and 845 (py-H4) ppm The

infrared spectrum displayed absorptions assigned to the νC-N absorption and two νC-S

40

bands These were observed at 1434 and 987 and 998 cm-1 respectively and were

taken to indicate formation of the dithiocarbamate moiety (along with the absence of

the N-H absorption) The mass spectrum (ES -ve) displayed a molecular ion for [M]-

at mz 274

Figure 222 Synthesis of monometallic complexes All charged complexes are hexafluorophosphate salts

41

To assess the coordination chemistry of the dithiocarbamate ligand 1 a range of

monometallic complexes was prepared taking advantage of the different electronic

properties of the metals chosen to obtain different molecular geometries around the

metal centre (Figure 222) A gold complex bearing the KS2CN(CH2py)2 ligand was

obtained by the reaction of [AuCl(PPh3)] with 1 to yield [Au(S2CN(CH2py)2)(PPh3)] (2)

The νC-S absorption band at 994 cm-1 suggested that the DTC was successfully

coordinated to the Au(I) centre The formation of a new complex was evident from a

new singlet resonance in the 31P1H NMR spectrum for the PPh3 ligand observed at

356 ppm shifted from the signal of the precursor (332 ppm) The 1H NMR spectrum

displayed the expected singlet resonance for the ethylene protons (NCH2Py) at 537

ppm alongside the triphenylphosphine and py-H3 resonances which appeared in the

aromatic region The resonances of the other protons of the picolyl moieties were

observed at 858 774 and 723 ppm and these were assigned to py-H4 py-H6 and py-

H5 respectively The overall structure of 2 was also confirmed by a molecular ion in

the electron spray mass spectrum (+ve mode) at mz 734 and good agreement of

elemental analysis with calculated values (closer than plusmn 05 to the calculated value)

Ligand 1 was treated with cis-[PtCl2(PPh3)2] in the presence of excess NH4PF6 in

methanol and dichloromethane to yield [PtS2CN(CH2py)2(PPh3)2]PF6 (3) after 16

hours The 31P1H NMR spectrum showed a new singlet resonance at 148 ppm (JPPt

= 3290 Hz) The chemical shift in the 1H NMR displayed the expected resonances for

the H-py protons at 862 (py-H4) 773 (py-H6) and 715 (py-H5) ppm while py-H3

resonances were obscured in the aromatic region by the signals due to the phenyl

groups The ethylene protons (NCH2Py) appeared as a singlet at 495 ppm Further

proof of the formation of the complex was provided by a molecular ion observed in the

electrospray (+ve mode) mass spectrum at mz 994

The reaction of 1 with cis-[RuCl2(dppm)2] (dppm = 11-

bis(diphenylphosphino)methane) provided an example of an octahedral geometry in

the cationic species [RuS2CN(CH2py)2(dppm)2]PF6 (4) Initially the reaction was

conducted at room temperature however an analysis of the 13P1H NMR revealed

an incomplete reaction probably due to the steric bulk of the picolyl groups The

reaction mixture was therefore heated at reflux for 4 hours to yield the product as a

dark yellow precipitate 4 in excellent yield (94) The retention of νC-N and νC-S features

in the infrared spectrum was observed with absorption bands at 1483 and 999 cm-1

42

respectively As expected broad multiplet resonances due to the methylene protons

(PCH2P) of the dppm were observed at 448 and 491 ppm in the 1H NMR spectrum

while all the picolyl protons signals were obscured in the aromatic region except for

py-H4 which was detected further downfield (861 ppm) The ethylene protons

(NCH2Py) were observed to resonate as two doublets at 468 and 521 ppm The

retention of the dppm ligands was further confirmed by the presence of two new

pseudotriplets at 51 and -188 ppm showing a coupling of 344 Hz in the 31P1H NMR

spectrum The overall structure of 4 was confirmed by a molecular ion in the

electrospray mass spectrum (+ve mode) at mz 1144 for [M]+ and good agreement of

elemental analysis with the calculated values

Two neutral Ru(II) complexes bearing this DTC ligand were prepared by treating the

precursor [Ru(R)Cl(CO)(BTD)(PPh3)2] (R = CH=CHC6H4Me-4 or CH=CHPyr-1 BTD =

213-benzothiadiazole) with 1 at room temperature to yield [Ru(CH=CHC6H4Me-

4)(S2CN(CH2py)2)(CO)(PPh3)2] (5) and [Ru(CH=CHPyr-

1)S2CN(CH2py)2(CO)(PPh3)2] (6) The successful formation of the new products was

evidenced by the retention of the carbonyl group signal at approximately 1900 cm-1 in

the IR spectrum A new singlet resonance was observed at 386 and 380 ppm for 5

and 6 respectively in the 31P1H NMR spectrum suggesting that the mutually trans

arrangement of the phosphines was retained and confirming the plane of symmetry of

the complex In the 1H NMR spectrum characteristic resonances for the Hα and Hβ

protons of the vinyl ligands were observed at new chemical shifts of 769 and 542

ppm (JHH =166 Hz JHP = 34 Hz) and 834 (JHH = 170 Hz JHP = 32 Hz) and 679 ppm

for 5 and 6 respectively The ethylene arms (NCH2Py) of the DTC unit gave rise to a

pair of singlets (5 446 467 ppm 6 454 469 ppm) for both complexes Mass

spectrometry analysis of the complexes revealed molecular ions at mz 1046 (5) and

mz 1131 (6) confirming the overall formulation of the products in conjunction with

good agreement of elemental analysis with the calculated values

A single crystal of 5 was grown by the solvent layering technique with the slow

diffusion of diethyl ether into a concentrated dichloromethane solution of the complex

yielding crystals A colourless needle was chosen for the structural determination

(Figure 223) The structural features of the complex are comparable to those of

related molecules reported in the literature17 such as [Ru(CH=CHC6H4Me-

4)S2CN(CH2CH2OMe)2(CO)(PPh3)2] A distorted octahedral geometry is observed in

43

the crystal structure of 5 with cis-interligand angles in the range 6983(3) to 9739(3)˚

Furthermore the angle of P(1)-Ru-P(2) is forced to deviate from linearity to 16869(3)˚

due to the bulkiness of the picolyl group Another noteworthy feature is that the Ru-S

distances of 24740(8) and 25025(8) Aring are longer than those reported in the literature

complex above reflecting the substantial trans effect of carbonyl and alkenyl ligands

The S(1)-C(2)-S(3) angle of 11319 (18)˚ in 5 is very similar to the 11347(10)˚ angle

found in [Ru(CH=CHC6H4Me-4)S2CN(CH2CH2OMe)2(CO)(PPh3)2]17 The relatively

short C(2)-N(4) (1333(8) Aring) distance in 5 suggests multiple bond character which

confirms the substantial delocalisation provided by the contribution of the thioureide

resonance form in the DTC ligand

Figure 223 The molecular structure of [Ru(CH=CHC6H4Me-4)S2C-N(CH2py)2(CO)(PPh3)2] (5) The H-atoms has been omitted to aid clarity

The reaction of an excess of 1 in methanol with the five-coordinate ruthenium enynyl

species [RuC(CequivCPh)=CHPhCl(CO)(PPh3)2] in dichloromethane resulted in the

44

formation of the yellow solid [RuC(CequivCPh)=CHPhS2C-N(CH2py)2(CO)(PPh3)2] (7)

in 77 yield after 2 hours at reflux The presence of the enynyl ligand was confirmed

by the absorption at 2145 cm-1 (νCequivC) in the infrared spectrum while the carbonyl group

gave rise to a band at 1915 cm-1 A singlet resonance for the vinylic proton was

observed in the 1H NMR spectrum at 610 ppm and assigned to the Hβ proton while

the resonances due to the methylene protons (NCH2Py) were observed as two singlets

at 461 and 441 ppm Only py-H4 was observed to resonate at 844 ppm whereas the

other picolyl protons resonances were obscured in the aromatic region by resonances

due to the phenyl groups of the various ligands 31P1H NMR spectroscopy revealed

a singlet resonance which was taken as evidence of the retention of the phosphine

ligands at 361 ppm Elemental analysis and mass spectrometry (ES +ve mode) data

confirmed the overall formation of 7

The focus of the investigation then turned to homoleptic compounds with the

generation of the complex [Ni(S2C-N(CH2py)2)] (8) by reaction of 1 with NiCl2middot6H2O in

methanol for 3 hours at room temperature No significant change compared to the

precursor was registered in the infrared spectrum 1H NMR analysis revealed signals

for the ethylene arms (NCH2Py) shifted from 557 ppm to 502 ppm Unremarkable

shifts were recorded for the four proton resonances of the picolyl substituents py-H5

(725 ppm) py-H3 (738 ppm) py-H6 (772 ppm) and py-H4 (858 ppm) Mass

spectrometry analysis (electrospray +ve mode) revealed an abundant molecular ion

at mz 607 for [M+H]+ confirming the formation of 8

Subsequently the focus of the research moved to the generation of multimetallic

complexes by employing compound 4 as a starting point due to the availability of

pendant nitrogen donors that would theoretically coordinate strongly with a transition

metal while the inertness of the dppm ligand would ensure the stability of the remaining

coordination sphere Unfortunately the reaction of 4 with [ReCl(CO)5] [W(CO)4(pip)2]

(pip = piperidine) or [Mo(CO)6] did not show clear evidence of formation of a complex

of interest even under forcing conditions (reflux) This finding might suggest that the

nitrogen coordination lsquopocketrsquo is too small to accommodate the bulk of rhenium

molybdenum or tungsten units

In conclusion the dithiocarbamate ligand 1 was successfully employed to synthesise

a range of monometallic complexes displaying linear square planar and octahedral

45

geometries Further modification to install a different metal unit (Re Mo and W) in the

most stable complex 4 proved unsuccessful

23 Heteromultimetallic complexes bearing a polyfunctional dicarboxylate

ligand

The second part of this chapter is based on the application of commercially-available

and simple ligands possessing both oxygen and nitrogen donor groups for the

generation of multimetallic systems This will be achieved by exploiting the different

donor properties of the terminal functionalities towards specific metal centres In this

work the different reactivities of oxygen and nitrogen in 22rsquo-bipyridine-44rsquo-

dicarboxylic acid (H2dcbpy) were explored with ruthenium and rhenium precursors

Dicarboxylic acids are commonly used in the construction of multimetallic assemblies

and are well established ligands in coordination polymers10 and metal-organic

frameworks (MOFs)1819 A summary of the synthesised complexes is provided in

Figure 231

The ruthenium vinyl [Ru(CH=CHC6H4Me-4)Cl(CO)(PPh3)2] and enynyl

[RuC(CequivCPh)=CHPhCl(CO)(PPh3)2] complexes were chosen as a starting point for

the generation of multimetallic assemblies due to their diagnostic spectroscopic

features Our previous studies142021 have demonstrated the formation of

corresponding octahedral carboxylate complexes when the complexes are

coordinated to the deprotonated carboxylic acid However both of the ruthenium

precursors above also react with bipyridine to yield the cationic complexes

[Ru(CH=CHC6H4Me-4)(CO)(bpy)(PPh3)2]+ and

[RuC(CequivCPh)=CHPh(CO)(bpy)(PPh3)2]22 For this reason it is not immediately clear

whether the H2dcbpy ligand would react with ruthenium precursors at the nitrogen or

at the oxygen donors or both

46

Figure 231 Synthetic routes to compounds 9 to 16

It is known20 that the presence of a base in the reaction mixture will prevent the acid-

driven cleavage of the vinyl group The neutral bimetallic ruthenium complex

[RuCH=CHC6H4Me-4)(CO)(PPh3)22(micro-dcbpy)] (9) was isolated as a brown powder

through the reaction of H2dcbpy with two equivalents of [Ru(CH=CHC6H4Me-

4)Cl(CO)(BTD)(PPh3)2] (BTD = 213-benzothiadiazole) in the presence of excess

base By employing a similar synthetic procedure H2dcbpy was treated with two

equivalents of the more sterically-hindered [RuC(CequivCPh)=CHPhCl(CO)(PPh3)2] to

yield after purification the bimetallic complex

[Ru(C(CequivCPh)=CHPh)(CO)(PPh3)22(micro-dcbpy)] (10) as a dark red compound

Standard analytical methods were employed to support the successful synthetic

procedure through comprehensive characterisation The 31P1H NMR spectrum for

47

both complexes 9 and 10 revealed a new singlet resonance at 382 ppm suggesting

the retention of the trans symmetrical disposition of the phosphine ligands of the

precursors Typical features attributed to the vinyl ligands in 9 were identified in the 1H

NMR spectrum with the methyl protons appearing at 223 ppm the aromatic protons

of the tolyl substituent (AArsquoBBrsquo system) at 635 and 682 ppm (JHH = 78 Hz) and the

vinyl protons Hβ and Hα were observed at 589 ppm and 782 ppm respectively (JHH

= 152 Hz) The coordination of the dcbpy ligand to the metal centre was confirmed by

new chemical shifts for the six bipyridyl protons which exhibit a resonance at 692

(dd) 766 (m) and 846 (d) ppm The doublet resonance attributed to the two bipyridyl

protons remained further downfield (846 ppm)23 indicating that the bpy unit remains

uncoordinated to the ruthenium centre

In addition the 1H NMR of complex 10 showed six pyridinyl protons resonating at

similar chemical shifts to those of 9 while the aromatic protons of the enynyl ligand

were superimposed on the signals from the phosphine ligands The most compelling

feature of the spectra was the peak for the vinyl proton (Hβ) at 579 ppm which

required a low-temperature experiment to be observed clearly due to extensive

broadening Moreover both complexes showed characteristic absorbances for

coordinated carbonyl moieties (9 1928 cm-1 10 1929 cm-1 ) and coordinated

carboxylates (9 1573 cm-1 10 1522 cm-1) in the infrared spectra Additionally the

presence of the triple bond CequivC in complex 10 was established by the absorbance at

2163 cm-1 The elemental and mass spectra data further confirmed the overall

formulation

To better explore the coordinative possibilities of the [dcbpy]2- ligand a different and

more robust starting material cis-[RuCl2(dppm)2] was employed The chloride ligands

are easily removed to generate a pair of reactive sites available to coordinate [dcbpy]2-

without affecting the remaining coordination sphere due to the inertness of the dppm

ligand24 With this in mind a dichloromethane solution of cis-[RuCl2(dppm)2] was

added to the methanolic solution of H2dcbpy and sodium methoxide in the presence

of different counterion sources potassium hexafluorophosphate and sodium

tetraphenylborate to yield [Ru(dppm)22(micro-dcbpy)](PF6)2 (11) and [Ru(dppm)22(micro-

dcbpy)](BPh4)2 (12) respectively

48

The spectroscopic data for both complexes show minor incongruences which can be

attributed to the small differences in electronic perturbance between [PF6]macr and

[BPh4]macr In the 31P1H NMR spectrum a dramatic shift of phosphorus nuclei

resonance was observed for 11 ( -119 and 87 ppm JPP = 388 Hz) and 12 (-116 and

88 ppm JPP = 392 Hz) compared to the precursors (-270 and -09 ppm JPP = 361

Hz) This difference is caused by the substantial change in coordination and charge

around the metal centre with the substitution of the two negatively charged chloride

ligands for the single negatively charged carboxylate chelate

Moreover the 1H NMR spectrum of compound 11 revealed a diagnostic resonance for

the PCH2P methylene bridges of the dppm ligands at 416 and 476 ppm slightly

different to those of compound 12 (393 and 456 ppm) Also singlet (11 855 ppm

12 851 ppm) and doublet (11 891 ppm 12 880 ppm) splitting patterns further

downfield could be discerned for the protons of the dcbpy ligand The presence of

coordinated carboxylate moiety in both complexes was confirmed by the diagnostic

absorption peaks in the infrared spectra (11 1521 cm-1 12 1509 cm-1) The mass

spectrometry and elemental analysis confirmed the overall formulation of both

complexes

Several attempts to crystalise compounds 9-11 to provide crystals suitable for X-ray

analysis proved unsuccessful Variation of the counterion in 12 from PF6macr to the bulkier

BPh4macr led to the successful generation of single crystals suitable for analysis (Figure

232) Yellow needles of 12 were obtained by slow diffusion of diethyl ether into a

dichloromethane solution of the compound The structural features of the crystal are

in agreement with those of similar molecules reported in the literature such as

[Ru(O2CMe)(dppm)22](BPh4)225 The geometry of the complex is influenced both by

the constraints of the three bidentate ligands which coordinate to the ruthenium centre

creating four-membered rings and by the high steric demand of dppm ligand

especially the phenyl moieties These effects can be seen in the distorted octahedral

geometry of 12 where the angle O(3)-Ru(1)-O(1) of the carboxylate moiety is

5979(15)˚ The intraligand angles due to dppm coordination P(13)-Ru(1)-P(11) and

P(43)-Ru(1)-P(41) are 7170(6)˚ and 7245(6)˚ respectively whereas the cis-

interligand angles O(1)-Ru(1)-P(11) and O(1)-Ru(1)-P(13) were found to be 9023(11)˚

and 10841(1)˚ which again deviate from the 90˚ of a regular octahedron Another

49

noticeable feature is that the axial Ru-P bonds are longer [23361(16)˚ and 23570(16)˚

Aring] than those trans to the oxygen donors [22640(16)˚ and 22916(17)˚ Aring] probably

due to a weak trans effect The influence of the steric hindrance of the dppm ligand

was also observed in the difference in bond length between the two oxygen atoms and

the ruthenium centre Ru(1)-O(3) is 2161(4)˚ Aring and Ru(1)-O(1) is 2232(4)˚ Aring The rest

of the bond distances are unremarkable

Figure 232 Structure of cation [Ru(dppm)22(micro-dcbpy)](BPh4)2 (12) The tetraphenylborate anion and H-atoms has been omitted to aid clarity

The discovery of rhenium pentacarbonyl halides by the action of carbon monoxide on

the corresponding hexahalogenorhenates26 was first reported by Schulten in the late

1930s Since then this class of compound has been used as a synthon for various

substitution reactions especially with diamine donors In this contribution the known

[ReCl(CO)3(micro-H2dcbpy)] complex was treated with compounds 9 - 11 to generate

heteromultimetallic complexes by coordinating the rhenium centre with the nitrogen

donors of the dcbpy ligands Regardless of the extreme conditions (reflux in toluene)

50

employed no trimetallic compound could be obtained The crystal structure of 12

reveals that the nitrogen atoms of the dcbpy ligand preferentially take up positions with

the nitrogen atoms orientated in opposite directions requiring a rotation around the

C6-C6(A) bond to allow the bidentate coordination of the rhenium(I) centre possibly

explaining the difficulties in the synthesis

A different strategy was therefore devised to obtain the trimetallic compounds This

new approach required the synthesis of the known orange complex [ReCl(CO)3(micro-

H2dcbpy)] (13)27 as a starting point for further transformation A methanolic solution of

13 and sodium methoxide was treated with two equivalents of either

[Ru(CH=CHC6H4Mendash4)Cl(CO)(BTD)(PPh3)2] or [RuC(CequivCPh)=CHPhCl

(CO)(PPh3)2] to give respectively [Ru(CH=CHC6H4Mendash4)(CO)(PPh3)22(micro-

[ReCl(dcbpy)(CO)3])] (14) and [RuC(CequivCPh)=CHPh(CO)(PPh3)22(micro-

[ReCl(dcbpy)(CO)3])] (15) Proton-decoupled phosphorus-31 NMR spectra of both

complexes did not show significant differences compared to the bimetallic

counterparts (9 and 10) validating the synthetic procedure However the 1H NMR

spectrum of 14 showed a slight shift in the bpy protons (701 726 868 ppm)

compared to 9 (692 766 and 846) Also the 1H NMR spectrum of 15 indicated a

slight change of chemical shift for the resonance assigned to the bpy protons (689

and 866 ppm) compared to 10 (692 and 846 ppm) The infrared data revealed the

presence of the characteristic absorptions for the tricarbonyl-rhenium moiety at 2019

and 1890 cm-1 while the (CO) peaks for the carbonyl ligands coordinated to the

ruthenium centres shifted to 1918 (14) and 1919 (15) cm-1 Mass spectra and

elemental analysis confirmed the hypothesised composition

The series of trimetallic complexes was completed by reaction of 13 with two

equivalents of cis-[RuCl2(dppm)2] to yield [Ru(dppm)22(micro-ReCl(dcbpy)(CO)3)]

(PF6)2 (16) The 31P1H NMR analysis showed no significant shift with respect to the

corresponding bimetallic compound 11 However in the 1H NMR spectrum the

doublet of bipyridyl protons resonating further downfield at 918 ppm (11 891 ppm)

provided further proof for the coordination of the chlorotricarbonyl-rhenium unit The

IR spectrum further confirmed the presence of carbonyl ligands coordinated to the

rhenium centre (peaks around 2020 cm-1)

51

In conclusion this work illustrates the use of polyfunctional linkers comprising nitrogen

and carboxylic acid donors for the generation of a series of bi- and trimetallic

complexes of Re(I) and Ru(II) in a controlled stepwise manner

24 Multimetallic complexes based on polyfunctional ligands (sulfur and

nitrogen)

The last part of this chapter will discuss the stepwise generation of multimetallic

assemblies by taking advantage of the different reactivity of sulfur and nitrogen donors

of 4-mercaptobenzoic acid in both thiolate and disulfide forms to generate novel

ruthenium and gold complexes Well-known ruthenium vinyl and enynyl complexes will

be employed as starting points for the generation of multimetallic networks possessing

ligands with diagnostic spectroscopic properties (1H 13C 31P NMR and IR

spectroscopy) to aid structure determination However under certain conditions (eg

the presence of acid) the vinyl species are sensitive to cleavage and there are also

potential stability and purification issues related to phosphine lability in the presence

of bulky co-ligands These concerns led to the use of a more robust ruthenium starting

material cis-[RuCl2(dppm)2] which also offers suitable spectroscopic (NMR

spectroscopy) features due to the presence of phosphorus nuclei and characteristic

methylene bridges of the dppm ligands

241 Synthesis of bi-and trimetallic complexes

A methanolic solution of iodine was added dropwise to 4-mercaptobenzoic acid in

methanol to yield the white disulfide product (SC6H4CO2H-4)2 (17) The aryl

resonances in the 1H NMR spectrum were observed at new chemical shift values (752

and 781 ppm JHH = 80) and the absence of a thiol resonance at 209 ppm confirmed

the completion of the reaction The other spectroscopic data were found to be in good

agreement with the data reported in the literature2829 The versatile ruthenium starting

material cis-[RuCl2(dppm)2]30 was employed as a starting point to generate a

multimetallic complex due to the inertness of the dppm ligand contributing to the

stability of the coordination sphere upon displacement of the chloride ligands These

complexes were found to react with the deprotonated dicarboxylic acid units (sodium

52

methoxide) in the presence of a counterion to yield a new complex

[Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18) (Figure 241)

Figure 241 Synthesis of bi-and trimetallic complexes All charged complexes are hexafluorophosphate salts PPN = bis(triphenylphosphine)iminium

A high yield (86) of the pale yellow product (18) was achieved and the infrared

spectra displayed the characteristic features for the carboxylate and

hexafluorophosphate anion at 1590 and 834 cm-1 respectively The multiplet

resonances for the methylene protons (PCH2P) at 395 and 463 ppm in the 1H NMR

spectrum confirmed the presence of the dppm ligands whereas the C6H4 protons were

obscured by the aromatic resonances of the phenyl groups of the dppm ligands The


pseudotriplets at -120 and 89 ppm showing a coupling of 390 Hz in the 31P1H NMR

spectrum Three triplet resonances downfield at 1349 1419 and 1817 ppm were

assigned to CCO2 CS and CO2 nuclei in the 13C1H NMR spectrum Also the carbon

nuclei of the methylene bridge in the dppm ligands were observed to resonate at 436

ppm with JPC = 115 Hz The overall structure of 18 was also confirmed by a molecular

ion in the electrospray mass spectrum (+ve mode) at mz 2044 and good agreement

of elemental analysis with the calculated values

53

The generation of a yellow trimetallic complex [AuSC6H4CO2Ru(dppm)22]PF6 (19)

in 71 yield was accomplished by treatment of two equivalents of cis-[RuCl2(dppm)2]

with one equivalent of the homoleptic gold(I) dithiolate species [Au(SC6H4CO2H-

4)2]PPN (PPN = bis(triphenylphosphine)iminium)3132 in the presence of sodium

methoxide and NH4PF6 The chemical shifts in the 1H NMR spectrum displayed the

expected multiplet resonances for the PCH2P protons at 388 and 505 ppm which

are slightly shifted compared to those in compound 18 Formation of a new complex

was evident from two new pseudotriplet resonances for the dppm ligands observed at

-79 and 140 ppm in the 31P1H NMR spectrum showing mutual JPP coupling of 390

Hz The integration of this spectrum suggested a dppm to PF6minus ratio of phosphorus

nuclei of 81 indicating a single counteranion for the complex The mass spectrum

(ES +ve) did not display a molecular ion but instead exhibited a peak for [MndashAu]+ at

mz 2044 However the formulation of 19 was further confirmed by elemental analysis

which revealed a good agreement between experimental and calculated values

242 Synthesis of bi- and trimetallic vinyl complexes

Since the disulfide ligand (17) was observed to coordinate smoothly to the cis-

[RuCl2(dppm)2] unit the focus of the research was then shifted to prepare multimetallic

complexes bearing both alkenyl and enynyl ligands (Figure 242) The most

appropriate triphenylphosphine vinyl species chosen to use as starting materials are

the compounds [RuC(CequivCPh)=CHPhCl(CO)(PPh3)2]33 and [Ru(CH=CHC6H4Mendash

4)Cl(CO)(BTD)(PPh3)2]34 The insertion of 14-diphenylbutadiene and 4-

ethynyltoluene into [RuHCl(CO)(PPh3)3]35 proved to be a suitable route to for the

generation of [RuC(CequivCPh)=CHPhCl(CO)(PPh3)2] and [Ru(CH=CHC6H4Mendash

4)Cl(CO)(BTD)(PPh3)2] respectively In the latter case BTD (213-benzothiadiazole)

was added to prevent unwanted reaction with the third equivalent of PPh3 lost in the

synthesis Furthermore the characteristic spectroscopic properties (1H 13C 31P1H

NMR and IR spectroscopy) of these vinyl and enynyl species are important in deducing

the structure of the multimetallic assemblies formed

54

Figure 242 Synthesis of Bi- and Trimetallic vinyl complexes

In the presence of a base 4-mercaptobenzoic acid was treated with [AuCl(PPh3)] to

generate the thiolate compound [Au(SC6H4CO2H-4)(PPh3)] which displayed

comparable spectroscopic data to those reported in the literature3132 This gold thiolate

complex was then treated with [Ru(CH=CHC6H4Mendash4)Cl(CO)(BTD)(PPh3)2] in

dichloromethane to yield [(Ph3P)Au(SC6H4CO2-4)Ru(CH=CHC6H4Me-4)(CO)(PPh3)2]

(20) as a yellow solid The presence of two new singlets at 375 (RuPPh3) and 387

(AuPPh3) ppm was observed in the 31P1H NMR spectrum Furthermore 1H NMR

analysis demonstrated characteristic resonances for the vinyl ligands at 785 and 583

for Hα and Hβ protons (mutual JHH coupling of 154 Hz) respectively The Hα protons

resonated at lower field with a doublet of triplets splitting pattern showing coupling to

the phosphorus nuclei of the phosphine ligand (JHP = 26 Hz) suggesting a mutually

trans arrangement for the phosphines and confirming a plane of symmetry in the

complex The tolyl substituent displayed an AB spin system at 639 and 683 ppm with

JAB = 80 Hz while the methylene group was found to resonate further upfield at 223

ppm Another AArsquoBBrsquo spin system at 685 and 720 ppm (JAB = 83 Hz) was assigned

to the protons in the 4-mercaptobenzoic ligand (SC6H4)

Evidence from the 13C1H NMR spectrum provided further proof of the formation of a

heterometallic complex (20) showing two triplet resonances at 2071 and 1535 ppm

55

which were assigned to CO and Cα nuclei respectively Two singlets were observed

to resonate at 1782 and 1476 ppm and these were attributed to the CO2 and CS

units respectively The methylene carbon nucleus was recorded as resonating further

upfield at approximately 209 ppm The retention of the carbonyl group was confirmed

by the infrared spectrum through the intense absorption at 1908 cm-1 along with a

band at 1586 cm-1 attributed to the coordinated carboxylate group Although no

molecular ion was observed in the electrospray (+ve mode) mass spectrum an

abundant fragmentation was noted at mz 1481 for the molecular ion plus sodium and

potassium ions From these data and in conjunction with a good agreement of

elemental analysis with calculated values the overall formulation of the bimetallic

complex (20) was confirmed

Similarly the reaction of equal amounts of [Au(SC6H4CO2H-4)(PPh3)] and the five-

coordinate enynyl starting material [RuC(CequivCPh)=CHPhCl(CO)(PPh3)2] in

dichloromethane resulted in the formation of a yellow solid in 68 yield The presence

of the enynyl ligand was confirmed by the infrared spectrum absorption at 2163 cm-1

(CequivC) while the carboxylate linkage gave rise to a band at 1588 cm-1 (CO) An

expected broad singlet resonance observed at 608 ppm was assigned to the Hβ

proton while the resonances of all phenyl groups were noted in the aromatic region of

the 1H NMR spectrum Two singlet resonances for AuPPh3 and RuPPh3 were

observed in the 31P1H NMR spectrum at 371 and 375 ppm respectively Further

analyses by 13C1H NMR spectroscopy revealed diagnostic resonances for CO (2074

ppm) CO2 (1780 ppm) CS (1476 ppm) and Cα (1404 ppm) nuclei comparable to

the same features found for complex 20 Further analysis by electrospray (+ve mode)

mass spectrometry showed an abundant molecular ion at mz 1469 [M]+ Calculated

and experimental elemental analysis results were found to be in good agreement

confirming the overall composition of the complex to be [(Ph3P)Au(SC6H4CO2-

4)RuC(CequivCPh)=CHPh(CO)(PPh3)2] (21)

A supramolecular trimetallic assembly incorporating Re Ru and Au was prepared by

reaction of a slight excess of sodium methoxide with equimolar amounts of

[Au(SC6H4CO2H-4)(PPh3)] and [RuCH=CH-bpyReCl(CO)3Cl(CO)(BTD)(PPh3)2]36 to

produce [(Ph3P)Au(SC6H4CO2-4)RuCH=CHbpyReCl(CO)3(CO)(PPh3)2] (22) as an

intense orange solid Two closely spaced singlet resonances were observed in the

31P1H NMR spectrum at 379 and 380 ppm and were assigned to RuPPh3 and

56

AuPPh3 respectively The 1H NMR spectrum displayed typical resonances for the Hα

(892 ppm) and Hβ (578 ppm) protons showing a mutual JHH coupling of 156 Hz The

splitting pattern observed for Hα also displayed coupling to the phosphorus nuclei of

the phosphine ligand (JHP = 26 Hz) confirming a trans arrangement of the phosphines

in the complex Two AB systems at 692 and 721 ppm with a coupling of JAB = 85

Hz were assigned to the SC6H4 protons The presence of broad carbonyl absorption

bands at 2016 1909 and 1885 cm-1 in the infrared spectrum was ascribed to the

retention of the ReCl(CO)3 unit in the complex Although no molecular ion was

observed in the mass spectrum an abundant fragmentation was noted at mz 1793

for [M+H+K]+ The overall formulation of the product as [(Ph3P)Au(SC6H4CO2-

4)RuCH=CHbpyReCl(CO)3(CO)(PPh3)2] was confirmed by the good agreement of

elemental analysis with calculated values

Suitable orange block crystals of complex 22 were successfully grown by slow

diffusion of diethyl ether into a dichloromethane solution of the complex (Figure 243)

Discussion of the structure of the ReRuAu trimetallic complex will be divided into three

parts based on the individual metals using literature structures for comparison

Firstly the geometry of the rhenium centre is a distorted octahedron with cis-

interligand angles in the ranges of 7463(18) ndash 930(5)deg which are comparable to the

values for the precursor [ReCl(CO)3(bpyCequivCH)] reported in the literature [7473(11) ndash

8764(18)deg]37

Figure 243 Crystal structure of [(Ph3P)Au(SC6H4CO24)RuCH=CHbpyReCl(CO)3(CO)(PPh3)2] (22) The H-atoms has been omitted to aid clarity

57

Secondly taking [Au(SC6H4CO2H-4)(PPh3)]38 complexes as a comparison it was

observed that the Au-S distance in 22 [23027(16) Aring] was comparable to the reported

literature value [2313 (1) Aring] for the precursor In addition the Au-P distance in 22 is

slightly shorter [2255(2) Aring] than the monometallic complex [2276(1) Aring] Moreover

the coordination geometry of the gold atom in compound 22 deviates from linearity [P-

Au-S 17639(6)deg] slightly less than in the literature structure [P-Au-S 16895(4)deg] This

finding might be related to the occurrence of short aurophilic contacts (AumiddotmiddotmiddotAu

30756(2) Aring) in the literature structure in conjunction with packing effects that lead to

distortion of this angle14 As expected the ruthenium centre adopts a distorted

octahedral geometry with cis interligand angles in the range 592(2)minus1078(2)deg which

are comparable to the bite angle of the carboxylate chelate in the literature structure

of [RuC(CequivCPh)=CHPh(O2CC5H4N)(CO)(PPh3)2]21 There is a slight difference in the

rutheniumminusoxygen bond distances which reveal a longer Ru(1)minusO(3) bond trans to

the vinyl ligand [2233(4) Aring] compared to the Ru(1)minusO(1) bond trans to the carbonyl

[2191(4) Aring] due to a stronger trans effect

243 Synthesis of gold nanoparticles and surface functionalisation

Although Faraday39 first described colloidal gold in the 1850s the practical use of well-

defined gold nanoparticles only became a reality with the breakthroughs of Turkevich18

in the 1950s (reliable synthesis of well-defined gold nanoparticles) and the work by

Brust and Schiffrin40 (thiol-protected gold nanoparticles of well-defined size) in the

1990s Larger nanoparticles (diameter 15-100 nm) are accessible using the Turkevich

method which employs sodium citrate as a reducing agent and a temporary capping

agent before displacement by sulfur units However the turning point for the evolution

of gold nanoparticle chemistry was achieved by the establishment of Brust and

Schiffrinrsquos synthetic approach This method involves the transfer of HAuCl4 from an

aqueous solution to an organic solvent followed by the reduction of a gold salt by

NaBH4 The presence of alkanethiols as stabilisers leads to the generation of

nanoparticles with diameters between 3-10 nm

Gold nanoparticles functionalised with transition metal units are receiving increased

attention in the field of nanotechnology particularly regarding their applications in

58

catalysis and sensing41 Research in these areas has been driven by the idea that gold

nanoparticles can be decorated with bifunctional surface units containing sulfur groups

and which have termini capable of coordinating to transition metal units42 The most

dominant approach is the chemisorption of thiols on the surface of the gold which has

been shown to be useful in a multitude of applications43 The idea of attaching

ruthenium metal units to gold surfaces is driven by the established approach in which

the gold surface will break the RS-SR bond of the disulfide leading to the formation of

two gold-thiolate interactions at the surface44 The key aspect of using disulfides rather

than thiols is that the reactivity of disulfides with metal centres of medium valency (eg

divalent ruthenium) is low compared to the reactivity with a (formally) zerovalent gold

surface4245 In order to broaden the knowledge of the functionalization of metal

surfaces the investigation was also extended to the analogous functionalisation of

colloidal palladium The scope of the investigation is illustrated in Figure 244

Figure 244 Synthesis of functionalised gold and palladium nanoparticles bearing ruthenium surface units All charged complexes are hexafluorophosphate salts

244 Brust and Schiffrin method

The disulfide linkage in 18 was observed to be stable under all the synthetic conditions

used in this research unless targeted by a strong reducing agent This phenomenon

59

allows the development of the surface architecture of gold nanoparticles functionalised

with ruthenium metal units The approach popularised by Brust and Schiffrin was

employed with a minor modification A methanolic solution of HAuCl4middot3H2O was added

to a solution of 18 in methanol and stirred for 30 minutes at room temperature Freshly

prepared reducing agent NaBH4 in water was added dropwise to the mixture resulting

in a colour change from yellow to brown indicating the formation of gold nanoparticles

The mixture was stirred for another 3 hours in an ice bath equipped with an external

thermometer to maintain the reaction temperature at approximately 10 degC to control

the rate of reduction and heat production during the exothermic reaction The

temperature needs to be constant throughout the synthesis to ensure a homogenous

size of nanoparticles The nanoparticles were washed with water followed by

dichloromethane using a centrifugation technique to remove any unattached surface

unit and led to the formation of black nanoparticles of

Au29[SC6H4CO2Ru(dppm)2]PF6 (NP1) Transmission Electron Microscopy (TEM)

analysis revealed an average diameter of 29 nm (plusmn 02 nm) for the gold nanoparticles

(Figure 245)

Figure 245 Average diameter 29 plusmn 02 nm based on over 200 nanoparticles obtained from the TEM images

The product NP1 was dissolved in deuterated dimethylsulfoxide to allow NMR

analysis The 31P1H NMR spectrum showed the formation of new pseudoquartet

resonances at -186 and -32 ppm with JPP = 357 ppm which differed significantly from

the chemical shifts found in the spectrum of 18 (-127 and 93 ppm JPP = 357) The

presence of the dppm ligands was further confirmed by the presence of a multiplet

resonance for the methylene protons at dramatically shifted chemical shift values of

60

444 and 576 ppm (compared to 388 and 505 ppm for 2 in d6-dmso) The resonances

for the C6H4 unit were masked in the aromatic region by those of the dppm ligands It

is apparent from the displacement in the chemical shift values between 18 and NP1

that there are substantial changes in the local environments of the ruthenium units

when attached to the surface of gold Further analysis showed that the presence of

bands at 1575 cm-1 and 817 cm-1 in the infrared spectrum revealing the retention of

the carboxylate unit and the hexafluorophosphate counter anions in this material

respectively Moreover the results of Energy Dispersive X-ray spectroscopy (EDX)

analysis indicate that gold ruthenium sulfur phosphorus and oxygen are present in

NP1 (Figure 246)

Figure 246 EDX spectrum of NP1

Another significant finding was that the loss in mass for NP1 (425) after gradual

heating from 0 degC to 800 degC in a thermogravimetric analyser (TGA) could be correlated

to the elimination of all the lighter elements in the materials leaving only gold and

ruthenium (Figure 247) This allowed the calculation of the surface unit coverage in

the material This revealed an approximate 841 ratio between the gold and the

[SC6H4CO2Ru(dppm)2]PF6 surface units

61

Figure 247 TGA analysis of NP1

In order to broaden the surface unit investigation Inductively-Coupled Plasma Atomic

Emission Spectroscopy (ACP-AES) was employed However the findings were rather

disappointingly inconsistent with other experimental data such as TGA A likely

explanation for this is that the material is not completely soluble at the concentration

of aqua regia used as a standard for the analysis The literature suggests that the

complete dissolution of ruthenium compoundsmaterials can only be achieved through

a high-temperature fusion technique using a molten flux of NaOH-NaNO346

245 Turkevich method

Larger nanoparticles of diameter 10-100 nm are accessible using the Turkevich

method HAuCl4middot3H2O in water was thus heated at reflux for 20 minutes then an

aqueous solution of citrate was added to the reaction mixture and the stirring at room

temperature continued for another 3 hours Trisodium citrate was employed as a weak

reducing agent and temporary capping agent The reaction mixture was left overnight

in a refrigerator to allow the nanoparticles formed to settle The dark blue nanoparticles

obtained Au119[SC6H4CO2Ru(dppm)2]PF6 (NP2) were washed with water

methanol and dichloromethane to remove any uncoordinated surface units TEM

images illustrated the formation of nanoparticles with an average diameter of 119 nm

(plusmn 09 nm) based on over 200 nanoparticles (Figure 248)

0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

(

)

Temperature ()

62

Figure 248 TEM images of NP2

Parallel analysis by EDX (Figure 249) detected ruthenium and gold as well as

phosphorus sulfur fluorine and oxygen in the complexes The formation of

Au119[SC6H4CO2Ru(dppm)2]PF6 (NP2) was further confirmed using 31P1H and 1H

NMR spectroscopic data which revealed comparable chemical shift changes to those

observed for NP1 indicating that the ruthenium surface units experienced similar

significant changes to their local environment when attached to the gold surface

compared to those of the molecular precursor 18

One major issue in gold nanoparticle research concerns the interaction of thiols with

the surface and the subsequent disruption caused to the metal surface This is the so-

called lsquostaplingrsquo phenomenon predicted by theory and observed in crystallographic

studies which can lead to the loss of surface units as gold(I) dithiolates This

undesirable loss of surface functionality is a significant drawback4748 The

dichloromethane filtrate used to wash the gold nanoparticles was analyzed to

determine the presence of surface units of dithiolate [AuSC6H4CO2Ru(dppm)22]PF6

(19) However there was no evidence for the presence of dithiolates only unreacted

[Ru(dppm)2(O2CC6H4S-4)2](PF6)2

63

Figure 249 EDX analysis of NP2

The TGA data showed that 575 metallic residue (gold and ruthenium) remained

after heating while 425 of the mass loss was due to the surface units The ratio

between the gold and [SC6H4CO2Ru(dppm)2]PF6 surface units was therefore

calculated as approximately 681 (Figure 2410)


0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

64

246 Palladium nanoparticle surface functionalisation

Compound 18 was also used to functionalise palladium nanoparticles Under an inert

atmosphere the palladium precursor [PdCl2(NCMe)2] was reduced by lithium

triethylborohydride in the presence of the phase transfer agent tetraoctylammonium

bromide (TOAB)49 before addition of a mixture of compound 18 in dry tetrahydrofuran

and dry acetonitrile The product of this procedure was the palladium nanoparticles

Pd[SC6H4CO2Ru(dppm)2]PF6 (NP3) which were washed with methanol and

acetone to remove unreacted starting material and excess TOAB NMR Spectroscopy

was found not to be suitable to analyse NP3 due to their insolubility in all common

deuterated solvents However typical features attributed to the surface units were

observed in the solid state infrared spectrum as found for NP1 and NP2

Figure 2411TEM image of NP3

TEM analysis showed small nanoparticles with diameter 22 nm (plusmn 02 nm) (Figure

2411) EDX analysis (Figure 2412) further confirmed the presence of palladium and

ruthenium surface units Approximately 384 of lighter elements were lost in TGA

analysis leaving 616 palladium and ruthenium metallic residue (Figure 2413) This

suggested that the ratio of palladium to surface units is close to 151 indicating a

sparsely covered nanoparticle surface

65

Figure 2412 EDX images of NP3

Figure 2413 TEM analysis of NP3

0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

66

25 Conclusion

The generation of monometallic complexes with different geometries bearing the

dithiocarbamate ligand [KS2CN(CH2py)2] was successfully carried out Unfortunately

attempts to insert a second metal into the assemblies through the use of the potentially

bidentate nitrogen donor atoms was unsuccessful

This finding led to the exploration of the polyfunctional dicarboxylic ligand H2dcbpy as

a starting point for the synthesis of heteromultimetallic complexes based on ruthenium

and rhenium precursors The synthesis was successful in highlighting the strong

affinity of carboxylate and nitrogen moieties to coordinate ruthenium and rhenium

centres respectively

Lastly various bi- and a trimetallic complex consisting of ruthenium rhenium and gold

were synthesised by tuning the reactivity of sulfur and carboxylate donors of 4-

mercaptobenzoic acid A ruthenium complex containing a disulfide linker was then

successfully used as a straightforward precursor with which to functionalize the

surface of gold and palladium nanoparticles

67

26 References

1 X He F Herranz E C-C Cheng R Vilar and V W-W Yam Chem - A Eur J 2010 16 9123ndash9131


3 M Shibasaki M Kanai S Matsunaca and N Kumagai Acc Chem Res 2009 42 1117ndash1127

4 R Sherwood F Gonzagravelez de Rivera J H Wan Q Zhang A J P White O Rossell G Hogarth and J D E T Wilton-Ely Inorg Chem 2015 54 4222ndash4230

5 R Packheiser P Ecorchard T Ruumlffer and H Lang Chem - A Eur J 2008 14 4948ndash4960


7 J D E T Wilton-Ely D Solanki E R Knight K B Holt A L Thompson and G Hogarth Inorg Chem 2008 47 9642ndash9653

8 S Biniecki and S Kabzinska Ann Pharm Fr 1964 22 685ndash7

9 E J OrsquoNeil and B D Smith Coord Chem Rev 2006 250 3068ndash3080

10 H Arora and R Mukherjee New J Chem 2010 34 2357

11 J R Long and O M Yaghi Chem Soc Rev 2009 38 1213ndash1214

12 E Eskelinen S Luukkanen M Haukka M Ahlgren and T A Pakkanen J Chem Soc Dalt Trans 2000 16 2745ndash2752

13 S I Bezzubov Y M Kiselev A V Churakov S A Kozyukhin A A Sadovnikov V A Grinberg V V Emets and V D Doljenko Eur J Inorg Chem 2016 2016 347ndash354

14 J A Robson F Gonzagravelez De Rivera K A Jantan M N Wenzel A J P White O Rossell and J D E T Wilton-Ely Inorg Chem 2016 55 12982ndash12996

15 R Bond AM Martin Coord Chem Rev 1984 54 23ndash98

16 J H Kim I H Hwang S P Jang J Kang S Kim I Noh Y Kim C Kim and R G Harrison Dalton Trans 2013 42 5500ndash5507

17 S Naeem E Ogilvie A J P White G Hogarth and J D E T Wilton-Ely Dalton Trans 2010 39 4080ndash4089



20 Y H Lin L Duclaux F Gonzagravelez de Rivera A L Thompson and J D E T

68

Wilton-Ely Eur J Inorg Chem 2014 2014 2065ndash2072


22 K A Jantan J A McArdle L Mognon V Fiorini L A Wilkinson A J P White S Stagni N J Long and J D E T Wilton-Ely Heteromultimetallic compounds based on polyfunctional carboxylate linkers 2018

23 A Santos J Loacutepez A Galaacuten J J Gonzaacutelez P Tinoco and A M Echavarren Organometallics 1997 16 3482ndash3488

24 B P Sullivan and T J Meyer Inorg Chem 1982 21 1037ndash1040

25 E B Boyar P A Harding S D Robinson and C P Brock J Chem Soc Dalt Trans 1986 9 1771ndash1778

26 W Hieber and H Schulten Zeitschrift fuumlr Anorg und Allg Chemie 1939 243 164ndash173

27 J M Smieja and C P Kubiak Inorg Chem 2010 49 9283ndash9289

28 C E Rowland N Belai K E Knope and C L Cahill Cryst Growth Des 2010 10 1390ndash1398

29 L Guerrini E Pazos C Penas M E Vaacutezquez J L Mascarentildeas and R A Alvarez-Puebla J Am Chem Soc 2013 135 10314ndash10317


31 J D E T Wilton-Ely H Ehlich A Schier and H Schmidbaur Helv Chim Acta 2001 84 3216ndash3232

32 J D E T Wilton-Ely A Schier N W Mitzel and H Schmidbaur J Chem Soc Dalt Trans 2001 7 1058ndash1062

33 A F Hill and R P Melling J Organomet Chem 1990 396 C22ndashC24

34 M C J Harris and A F Hill Organometallics 1991 10 3903ndash3906

35 N W Alcock A F Hill and M S Roe J Chem Soc Dalt Trans 1990 1737ndash1740


37 A Toscani K A Jantan J B Hena J A Robson E J Parmenter V Fiorini A J P White S Stagni and J D E T Wilton-Ely Dalt Trans DOI101039c6dt03810g


39 M Faraday Philos Trans R Soc London 1857 147 145ndash181

40 M Brust M Walker D Bethell D J Schiffrin and R Whyman J Chem Soc Chem Commun 1994 0 801ndash802


69

42 P Ionita A Caragheorgheopol B C Gilbert and V Chechik J Am Chem Soc 2002 124 9048ndash9049


44 J Noh and M Hara Thin Solid Films 2000 16 14ndash17

45 P Ionita A Caragheorgheopol B C Gilbert and V Chechik Langmuir 2004 20 11536ndash11544

46 T Suoranta M Niemelauml and P Peraumlmaumlki Talanta 2014 119 425ndash429



49 I Quiros M Yamada K Kubo J Mizutani M Kurihara and H Nishihara Langmuir 2002 18 1413ndash1418

70



Platinum Group Metals (PGMs) are recognised as ldquocritical raw materialsrdquo1 due to their

rarity and their unique chemical and physical properties2 that lead to numerous

applications in industry One of the most promising applications of PGMs (particularly

Pt Pd and Rh) is the manufacturing of three-way catalytic converters (TWCs) in the

automotive industry These precious metals are dispersed in a washcoat coated with

the ceramic or metallic substrate in the exhaust stream to convert most of the harmful

gases (carbon monoxide unburned hydrocarbons and nitrogen oxide) generated from

incomplete combustion in automobile exhausts into harmless substances (nitrogen

carbon dioxide and water vapour)3 Unfortunately the catalytic converters deactivate

and lose their catalytic activities in approximately 8-10 years4 due to several factors

such as fouling5 poisoning6 thermal degradation7 and sintering8 over time The

disposal of used catalytic converters is an environmental issue as a considerable

quantity of the precious metal they contain is disposed of directly into landfills9

In conjunction with European Union legislation10 on the recovery of precious metals

from waste and pollution reduction different recovery processes have been explored

and developed The most well-established recovery processes to recover PGMs from

catalytic converters are known as a pyrometallurgical and hydrometallurgical process

The pyrometallurgical route requires an energy-intensive process involving multiple

complicated steps including crushing batching granulation and smelting (at high

temperature)11 This method is known to be unselective for noble metals (NMs)12 The

alternative the hydrometallurgical process offers better selectivity and predictability in

the extraction metals using strong oxidising agents and cyanide but the presence of

harmful reagents in waste water derived from the process raises concerns over

environmental safety12

As a replacement for these environmentally-unattractive processes sustainable

lixiviants such as dihalogendithioxamide compounds have been shown to be a

powerful oxidation system capable of recovering NMs from secondary sources13 This

method offers attractive features such as high efficiency of recovery of NMs in

71

conjunction with low environmental impact This approach is thus suitable for replacing

more energy intensive polluting and harmful methods that are used commercially14

Pioneering work by Serpe et al15 has demonstrated an effective method of Pd-

dissolution utilising organic compounds such as the NN-dimethylperhydrodiazepine-

23-dithione diiodine adduct (Me2dazdtmiddot2I2)15 This compound successfully acts as a

leaching agent which is selective for palladium in the presence of rhodium and

platinum in a model system designed to mimic spent TWCs under mild conditions

(methylethylketone solution 80 degC atmospheric pressure)15 (Figure 311) This

reaction produces the complex [Pd(Me2dazdt)2]I6 which requires conventional

thermal treatment to recover metallic palladium as the end product However this

process requires an energy-intensive step which destroys the ligands making it a less

practical technique for recycling palladium To solve this problem it is proposed to

utilise directly the [Pd(Me2dazdt)2]I6 complex obtained from the recovery process An

interesting possible application that has been explored is as a precursor to a Pd(0)

photocatalyst for hydrogen production4

Figure 311 Extraction of palladium as the [Pd(Me2dazdt)2]I6 salt

Pd(II) complexes are known to be excellent catalysts for C-H bond activation due to

their stability towards oxidation while generating an organometallic intermediate (C-

PdII bond) The use of different commercially-available oxidants offers many

possibilities allowing for different functional groups to be inserted into a C-PdII bond16

The Wilton-Ely group demonstrated the ability of novel Pd(II) complexes bearing

dithiocarboxylate ligands to efficiently catalyse the C-H functionalization of

benzo[h]quinoline to form 10-methoxybenzo[h]quinoline in good yield17 following the

catalytic condition employed previously by Sanford18

72

In this Chapter palladium(II) dithiooxamide complexes are obtained directly from the

recovery process of TWCs and were chosen as potential candidates for the C-H

activation of benzo[h]quinoline and 8-methylquinoline In order to obtain a broader

picture of the effectiveness of disulfur species a range of different Pd(II)

dithiocarbamate complexes was synthesised and characterised This includes homo-

and heteroleptic mono- and bimetallic complexes in conjunction with neutral and

cationic palladium species The results obtained will provide a comparison with a

previously reported study using traditional catalysts18 mainly commercially available

Pd(OAc)2 In addition the optimisation of the catalytic reaction conditions will be

conducted by varying three different factors Pd loading temperature and time In this

context the work described here will focus on lower temperatures (50 degC) and shorter

reaction times (2-24 h) using appropriate Pd loadings (1-5 mol) to enhance the

lsquogreen credentialsrsquo of the method

The work in this chapter was completed with the help of an MRes student Chuek Yee

Kwok All the data in this Chapter have been published in the journal Green Chemistry

in a paper entitled ldquoFrom recovered metal waste to high-performance palladium

catalystsrdquo19


The aims of this chapter were as follows

1 Synthesise and characterise a series of neutral and cationic homo- and

heteroleptic mono- and bimetallic palladium compound based on

dithiocarbamate and dithiooxamide ligand

2 Investigate the catalytic activity of the palladium complexes bearing disulfur

species towards C-H functionalization of benzo[h]quinoline to 10-alkoxy

benzo[h]quinoline and 8-methylquinoline to 8-(methoxymethyl)quinoline in the

presence of the oxidant PhI(OAc)2

3 Optimisation of catalytic reaction conditions based on milder and safer (low

temperature 50 degC) approach and over shorter (1-3 h) reaction time

73


A series of palladium(II) dithiocarbamate complexes [Pd(S2CNEt2)(PPh3)2]PF6 (23)

[Pd(S2CNEt2)2] (24) [(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2

(25)[(Ph3P)2PdS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2Pd(PPh3)2][PF6]2 (26) were

prepared The Pd(II) dithiooxamide complexes [Pd(Me2dazdt)2]I6 (27)

[PdI2(Me2dazdt)] (28) and [Pd(Cy2DTO)2]I8 (29) were obtained directly from the

recovery process All compounds were characterised and later tested as potential

homogeneous catalysts in the selective C-H functionalization reaction


Both monometallic palladium dithiocarbamate complexes 232021 and 242223 were

synthesised according to published routes (Figure 321) The heteroleptic palladium

complex (23) was synthesised by adding a dichloromethane solution of cis-

[PdCl2(PPh3)2] to a methanolic solution of sodium diethyldithiocarbamate in the

presence of KPF6 (potassium hexafluorophosphate) The reaction mixture was

refluxed for 5 hours to yield a yellow precipitate in 91 yield For 24 stirring one

equivalent of K2[PdCl4] with two equivalents of NaS2CNEt2 at room temperature led to

the formation of the yellow product in 85 yield Both complexes were analysed by

1H 31P1H NMR and infrared spectroscopy and the results obtained were in accord

with the literature data2021

The dipotassium salt of NNrsquo-bis(dithiocarboxy)piperazine [KS2CNC4H8NCS2K]2425

was prepared by treating an ethanolic mixture of piperazine and potassium carbonate

(KOH) with CS2 at low temperature for 30 minutes The generation of the novel

bimetallic complex 25 was successfully achieved by the addition of cis-[PdCl2(PPh3)2]

in dichloromethane to a methanolic solution of KS2CNC4H8NCS2K in the presence of

KPF6 resulting in the formation of a yellow product in good yield (79) The solid-

state infrared spectrum displayed characteristic absorptions for the triphenylphosphine

and the C-S units at 831 and 999 cm-1 respectively The diagnostic signal for the

dithiocarbamate ligand in the 1H NMR spectrum appeared as a singlet resonance at

392 ppm A singlet phosphorus resonance for the PPh3 ligand was observed at 305

ppm in the 31P1H NMR spectrum while the 13C1H NMR spectrum showed the

74

expected singlet resonance at 206 ppm for the CS2 unit of the dithiocarbamate (DTC)

ligand An indicative fragmentation at mz 749 for [M2 + 3MeCN + 2H]+ was observed

in the mass spectrum under electrospray conditions in +ve mode The formulation of

25 was further confirmed by elemental analysis which revealed a good agreement

between experimental and calculated values

Figure 321 Synthesis route to palladium complexes with chelating dithiocarbamates

An aqueous solution of potassium hydroxide was added dropwise to a mixture of NNrsquo-

dibenzylethylenediamine and carbon disulfide in water to yield

KS2CN(Bz)CH2CH2N(Bz)CS2K26 This ligand was treated with cis-[PdCl2(PPh3)2] in

the presence of a counterion to form [(Ph3P)2PdS2CN(Bz)CH2CH2N(Bz)

CS2Pd(PPh3)2][PF6]2 (26) as a yellow powder The characterisation by infrared

spectroscopy revealed typical absorptions for the triphenylphosphine ligands in the

complex The 1H NMR spectrum displayed two singlet resonances at 362 and 456

ppm which were attributed to the ethylene bridge (NCH2CH2N) and benzyl methylene

group (PhCH2) respectively Distinct resonances for the phenyl ring were observed in

75

the aromatic region (ortho at 694 ppm meta at 717 ppm and para at 727 ppm) The

phosphorus nuclei were observed as a pair of doublets at 305 and 309 ppm with a

mutual coupling of 325 Hz In the 13C1H NMR spectrum the ethylene groups

NCH2CH2N and CH2Ph were observed to resonate at lower field at 451 and 539 ppm

respectively while a singlet at higher field at 207 ppm was attributed to the CS2 unit

The overall formulation of 26 was confirmed by an abundant molecular ion in the

electrospray (+ve ion) mass spectrum at mz 826 and by good agreement of the


322 Structural discussion

Single crystals of both novel bimetallic palladium dithiocarbamate complexes were

grown successfully by the solvent layering technique and structural studies were

undertaken The structures are shown in Figure 322 and Figure 323 Only selected

protons are shown and all counteranions are omitted

3221 The X-ray crystal structure of complex 25

[(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25) was crystallised in two different

polymorphs in the same sample (NMR tube) The yellow block monoclinic crystal of

25-A (Figure 322) and yellow block triclinic crystal of 25-B (Figure 323) displayed

the most common binding mode of dithiocarbamate ligands to form square planar

complexes The piperazine linker for both crystal structures adopts a chair

conformation similar to the complexes [(Ph3P)2Pt2(S2CNC4H8NCS2)](PF6)227 and

[(dppf)2Pd2(S2CNC4H8NCS2)](PF6)227

76

Figure 322 The structure of the cation present in the crystal of 25-A The hexaflorophosphate anions and H-atoms has been omitted to aid clarity

Figure 323 Structure of the cation present in the crystal of 25-B The hexaflorophosphate anions and H-atoms has been omitted to aid clarity

It is apparent from the data in Table 321 that the S-M-S bite angles of the

dithiocarbamate ligand in the new complexes lie in the range 7504(4) - 7536(3)˚

which are comparable to those of the complex [(dppf)2Pd2(S2CNC4H8NCS2)](PF6)2

(7518(5)˚) Also the S-C-S angle for 25-A and 25-B complexes has an average value

of 112˚ which is similar to previously reported palladium examples and the PdS2CN

unit is found to be planar in both cases The C-N distance for 25-A is slightly shorter

77

(1302(5) Aring) compared to 25-B (1326(4) Aring) but both are close to the typical average

C-N distance for dithiocarbamate complexes (1324 Aring)28 Furthermore the average C-

S bond lengths for 25-A and 25-B is 173(4) Aring and 172(4) Aring respectively which are

close to the typical average for dithiocarbamate complexes (1715 Aring)28 The average

Pd-S distance for 25-A and 25-B (2343(9) Aring) is very close to the palladium examples

in the literature (2347 Aring) Overall there is a slight deviation from planarity for the

dithiocarbamate ligand at the palladium metal centre in both complexes which can be

traced to the effect of sterically demanding co-ligands such as PPh3 and dppf27

Table 321 Data for the complexes [L2M(S2CNC4H8NCS2)ML2]2+

ML2 substituent M-S Aring C-N Aring C-S Aring S-C-S˚ S-M-S ˚

Pt(PPh3)2

27

2354(1) 2355(1)

1318 (6)

1723(5) 1725(5)

1118(3)

7467 (4)

Pd(dppf)27

23370(1) 2358(1)

1322(6)

1725(5) 1735(5)

1121(3)

7518(5)

Pd(PPh3)2 (25-A)

23304(10) 23536(10)

1302(5)

1722(4) 1735(4)

1112(2)

7504(4)

Pd(PPh3)2 (25-B)

23388 (8) 23479(9)

1326(4)

1714(4) 1727(4)

11276(19)

7536(3)

3222 The X-ray crystal structure of 26

A yellow tablet-shaped crystal of the dipalladium dicationic complex

[(Ph3P)2PdS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2Pd(PPh3)2] [PF6]2 (26) was grown by

slow diffusion of diethyl ether into a concentrated solution of the complex in acetone

(Figure 324)

78

Figure 324 The structure of the cation present in the crystal of 26 The hexaflorophosphate anions and H-atoms has been omitted to aid clarity

The compound [(dppf)PdS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2Pd(dppf)](PF6)226 can

be compared directly to complex 26 (Table 322) Complex 26 displays unsymmetrical

chelation of the metal to the dithiocarbamate ligand compared to the literature

complex which shows only small differences in its M-S and C-S distances In addition

the average C-N bond length (13195(9) Aring) recorded for 26 is comparable to typical

values for dithiocarbamate complexes of group 10 metals The S-M-S bite angle and

S-C-S angle value found in 26 are close to those of the literature complex perhaps

due to the presence of the slightly greater bulk of PPh3 vs dppf

Table 322 Data for the complexes [L2MS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2ML2]2+


Pd(dppf)26

23348(6) 23516(6) 23347(6) 23445(7)

1313(3) 1323(3)

1728(2) 1719(2) 1709(2) 1723(2)

11188(14) 11215(13)

7507(2) 7498(2)

Pd(PPh3)2 (26)

23720(16) 23190(15) 23735(17) 23180(15

1323(8) 1316(9)

1715(7) 1718(6) 1722(7) 1727(7)

1132(4) 1119(4)

7528(5) 7505(5)

79


The interaction of sulfur donors with a suitable acceptor such as diiodine in charge-

transfer adducts has been shown to provide powerful reagents for the oxidation of

metal powders29 The studies conducted by Serpe et al14 have demonstrated that

diiodine adducts of cyclic dithiooxamides which consist of soft donor atoms (iodine)

and the chelating properties of two vicinal thiones are capable of stabilising oxidised

d8 complexes of gold and palladium The most effective adduct Me2dazdtmiddot2I2 was

employed as a leaching agent to selectively extract palladium without reacting with the

other elements present in the ceramic support of spent catalytic converters such as

platinum and rhodium15 However the reduction of these compounds back to metallic

palladium requires an energy-intensive process This has encouraged us to explore

the ability of applying directly the palladium dithiooxamide complexes obtained in this

case as a catalyst in a C-H functionalization reaction

The reaction of two equivalents of Me2dazdtmiddot2I2 with palladium powder in acetone at

room temperature yielded [Pd(Me2dazdt)2]I6 (27) in very good yield (92) Diffusion of

diethyl ether into a concentrated acetone mixture of the complex successfully led to

flat black crystals of 27 The infrared and 1H NMR data were found to be in a good

agreement with literature values15 The heteroleptic complex [PdI2(Me2dazdt)] (28)

was obtained as a by-product (6) of this leaching process by re-crystallisation of the

crude mixture with Et2O (Figure 325) Using ligand substitution reactions hetero- (23)

and homoleptic (24) palladium dithiocarbamate complexes were prepared by the

reaction of 28 with sodium diethyldithiocarbamate and triphenylphosphine

80

Figure 325 Preparation of Pd(II) dithiooxamide complexes (n = 1 or 3)

Despite its success in the leaching process the synthesis of Me2dazdtmiddot2I2 requires

expensive (and evil-smelling) starting materials It was therefore decided to employ an

alternative and inexpensive acyclic secondary dithiooxamide ligand known as NNrsquo-

dicyclohexyl-dithiooxamide (Cy2DTO) to substitute the cyclic ligand Compound 29

[Pd(Cy2DTO)2]I8 was prepared by treating the acyclic Cy2DTO ligand with palladium

powder in ethyl acetate in the presence of iodine as an oxidant Red-brown crystals of

29 were obtained in good yields (70) by diffusion of Et2O into a concentrated acetone

mixture of the complex

33 Catalytic activity

The first substantial investigations of C-H functionalization catalysed by Pd(II)

complexes emerged during the 2000s Sanford and co-workers18 reported the C-H

functionalization of benzo[h]quinoline to 10-alkoxybenzo[h]quinoline (Figure 331

Reaction A) employing commercially available palladium acetate as a catalyst and

PhI(OAc)2 as a sacrificial oxidant The reaction was conducted in various alcohols to

81

produce a variety of alkyl-aryl ethers (R = Me Et Pri and CH2CF3) in a thick glass vial

at 100 degC with a reaction time typically between 18-27 hours

Figure 331 Oxidative C-H functionalisation reactions investigated in this work

Methoxylation of 8-methylquinoline (Figure 331 Reaction B) was also performed

under similar conditions Table 331 summarises the catalytic conditions and yields

for different substrates explored in the literature

Table 331 Literature conditions18 and yields for selective CndashH bond activation with different substrates using Pd(OAc)2 catalyst and PhI(OAc)2 as sacrificial oxidant at 100 degC

A significant breakthrough in the use of sulfur chelates to support these reactions was

achieved in the Wilton-Ely group17 This showed that a palladium complex bearing a

chelating dithiocarboxylate ligand was an active catalyst for this C-H activation

reaction Despite the prevailing assumption that sulfur ligands were less suitable to

support catalysis these complexes attained comparable catalytic results for Reaction

A to those found in the literature employing similar reaction conditions18 Using these

Reaction R Solvent [Pd] (mol) Time (h) Yield ()

A

Me MeOH 12 22 95

Et EtOH 51 24 80

Pri PriOHAcOH 33 27 72

CH2CF3 CF3CH2OH 13 21 71

B Me MeOH 19 18 80

82

findings as a proof of concept palladium complexes based on dithiocarbamate and

dithiooxamide units were tested as potential candidates for this homogeneous catalytic

reaction

331 Catalysis reaction conditions

The standard procedure for C-H functionalization proposed in the literature18 requires

the use of suitable high-pressure vials fitted with Teflon-lined caps which are heated

in an aluminium heating block at high temperature (100 degC) for the specified time

However heating a flammable organic solvent above its boiling point in the confined

space of the vial generates potential dangers related to pressure build-up In addition

it would be better to reduce the energy consumption from heating at high temperatures

overnight In this Section it will be demonstrated how these issues can be remedied

by optimising the reaction conditions employing temperatures below the boiling point

(50 degC) of the solvent and minimising the reaction time

For the reactions performed at 100 degC thick-walled vials with Teflon screw caps

equipped with an egg-shaped stir bar were used A blast shield was placed around the

setup as a precautionary measure Before re-using the thick vials and stir bars were

cleaned using aqua regia to ensure the removal of any palladium residue which might

affect the results of the catalytic reaction For the reactions conducted at 50 degC the

thick vials were replaced by commercially-available 14 mL thin-walled vials A drysyn

aluminium heating plate was used to provide constant heating allowing up to twelve

sample vials to be used for parallel reactions An electronic temperature regulator

connected to the heating plate was used to maintain the desired temperature before

the vials were inserted into the wells A second independent thermometer was also

inserted into a well to monitor the consistent heating throughout the experiment A

drop of silicone oil was added to ensure adequate heat transfer between the heating

block and vials

Benzo[h]quinoline was treated with the palladium catalyst in the presence of

(diacetoxy)iodobenzene [PhI(OAc)2] in the appropriate solvent A small amount of

sample was taken out and analysed by 1H NMR spectroscopy to determine the product

yields Since the reactions yielded no side products the yield of the product could be

83

determined by comparing the integration of resonances of H-2 (930 ppm) and H-10

protons (901 ppm) of benzo[h]quinoline with the diagnostic resonance of methoxy

(CH3) ethoxy (CH2CH3) or trifluoroethoxy (CH2CF3) groups which appeared at 419

163 and 445 and 474 ppm respectively in the alkoxy product Employing the same

protocols the yield of 8-(methoxymethyl)quinoline was determined by comparing the

integration of methyl resonances (282 ppm) of 8-methylquinoline with the resonances

of the methylene (519 ppm) and methoxy (357 ppm) groups in the product Three

experiments were conducted and the values averaged

To validate the 1H NMR integration method used to calculate the yield of product the

internal standard of 135-trimethoxybenzene was used in conjunction with the

integration of the 1H NMR spectrum of an equimolar mixture of pure benzo[h]quinoline

and 10-methoxybenzo[h]quinoline This revealed a small NMR spectroscopic error of

approximately 1-2 that confirmed the validity of the measurement method used In

addition an isolated yield of the product (for optimised conditions) was recorded after

scaling the experiment up and purifying using a flash column on silica which provided

further support to the yields determined by the 1H NMR integration method

332 Initial catalytic studies

To assess the potential of Pd(II) dithiocarbamate complexes as potential catalysts for

the proposed reaction (Figure 331 Reaction A) The complexes 23 24 25 and 26

were introduced to a vial along with benzo[h]quinoline and PhI(OAc)2 Methanol was

added to act as both reagent and medium and the reaction was performed following

literature18 conditions (100 degC 1 mol Pd loading 22 h) As can be seen in Figure

332 mono- (23 and 24) and bimetallic (25 and 26) palladium(II) dithiocarbamate

complexes proved to be active catalysts for the methoxylation of benzo[h]quinoline

producing the desired product in good yield (75 - 87) Moreover an analysis of the

1H NMR spectra obtained revealed that the reactions occur without any evidence of

byproducts

84

Figure 332 Methoxylation of benzo[h]quinoline using palladium dithiocarbamate complexes (1mol) Oxidant = PhI(OAc)2 T = 100 degC t = 2 and 22 h

With the objective of reducing the energy consumption for the catalytic reaction it was

decided to shorten the reaction time to two hours without changing any other

parameters Surprisingly an excellent yield of product was obtained approximately

87 69 87 and 84 for Pd(II) complexes 23 24 25 and 26 respectively This

unexpected but notable finding led us to try and optimise the conditions regarding

palladium loading and time to obtain the highest efficacy at the lowest environmental

impact

333 Standard operating conditions of palladium dithiocarbamate complexes

(SOCDTC)

The unexpected higher yield of methoxylation of benzo[h]quinoline at 50 degC reported

in Section 332 prompted us to adopt lower temperatures routinely for the catalysis

experiments These conditions are desirable both in terms of the safety implications

of heating organic solvent above its boiling point in a closed vessel as well as regarding

the energy consumption for heating purposes especially on a larger scale The

standard operating condition for palladium dithiocarbamate complexes (SOCDTC) was

86

75

8784

87

69

8784

0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Perc

enta

ge y

ield

(

)

Pd (II) dithiocarbamate complexes

22hr 2hr

85

determined by varying two different parameters the palladium loading and reaction

time

Complex 23 (1 mol) was used as a catalyst for the C-H functionalization of

benzo[h]quinoline in the presence of the oxidant in methanol to yield 96 of the

product after 22 hours reaction at 50 degC Contrary to expectations these findings are

comparable with those obtained employing Pd(OAc)2 at a higher temperature (100

degC) as reported in the literature18 (95 yield) The experiment was then repeated

under similar conditions but for shorter reaction time (2 h) leading to a lower yield

(36) of product In order to improve these results but keeping the reaction time at 2

hours a series of test reactions explored the impact of increasing the palladium

loading (from 2 to 5 mol) Figure 333 shows the clear incremental trend of the yield

corresponding to the increase in the palladium loading It is interesting to note how the

yield reaches a plateau at 3 mol loading of palladium with an almost complete

conversion (99) to the sole product

Figure 333 Methoxylation of benzo[h]quinoline at 50 degC Catalyst = 23 Oxidant = PhI(OAc)2 T = 50 degC t = 2 h

Further analyses were carried out using different Pd(II) dithiocarbamate catalysts (24

25 and 26) to determine the ideal loading for the catalytic reaction The results

obtained for the optimisation study are shown in Figure 334 The bar chart contains

revealing data Firstly unlike heteroleptic compound 23 homoleptic complex 24

30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Pd loading (mol)

86

showed lower catalytic activity giving a 73 conversion yield even at high loading (5

mol) This result can be explained by the presence of two anionic SS-chelating

dithiocarbamate ligands that are less labile compared to the monodentate

triphenylphosphine ligands in 23 These findings further support the proposed reaction

mechanism which postulates a labile triphenylphosphine ligand dissociates from the

Pd(II) coordination sphere Similarly it is also interesting to note that lowering the

temperature affected the performances of 24 due to the higher activation energy

barrier for the dissociation of the SS-chelate ligand which prevented higher yields of

product from being obtained

Figure 334 Table showing results for Reaction A using dithiocarbamate complexes 23 - 26 as catalysts R = Me solvent = MeOH oxidant = PhI(OAc)2 T = 50 degC t = 2 h

Furthermore it is somewhat surprising that the catalytic performances of the palladium

complexes 25 and 26 were comparable to that of 23 almost complete conversion was

achieved with a palladium loading of 3 mol suggesting that the bimetallic nature of

both complexes did not affect the performance of the catalyst It appears that the metal

centres simply act as two independent catalytically active palladium units rather than

showing any cooperativity as was initially anticipated19 Based on this catalytic

performance the standard operating conditions (SOCDTC) for these catalysts was set

at 3 mol Pd loading 50 degC for 2 hours

0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Yie

ld

)

Catalyst

1mol Pd 2mol Pd 3mol Pd 4mol Pd 5mol Pd

87

3331 Isolated yield investigation

To further confirm the successful formation of the product and to validate the 1H NMR

integration yield large-scale reactions of benzo[h]quinoline (150 mg) and 3 mol of

catalysts 23 and 26 in methanol were stirred at 50 degC for 2 hours (SOCDTC) All solvent

was removed under reduced pressure leading to the formation of a brown oil A flash

column on silica was employed to purify the product using a mixture of ethyl acetate

and hexane as the mobile phase The pale yellow solid 10-methoxybenzo[h]quinoline

was collected The yield was 172 mg (98) for catalyst 23 and 167 mg (95) for

catalyst 26 In both cases the integration of the 1H NMR spectrum reveals the

formation of the product in 99 yield


All the palladium dithiocarbamate complexes 23 - 26 were then tested as catalysts for

the formation of other alkoxybenzo[h]quinoline products (Reaction A) employing the

established SOCDTC conditions Changing the alcohol solvent used in the

transformation to ethanol a mixture of isopropanol and acetic acid and

trifluoroethanol respectively yielded the products 10-ethoxybenzo[h]quinoline 10-

isopropoxybenzo[h]quinoline and 10-trifluoroethoxybenzo[h]quinoline respectively A

different substrate 8-methylquinoline was also used to extend the investigation of C-

H functionalization to a different class of substrate (Reaction B)

The yields of the alkoxy products were calculated by integrating the 1H NMR spectra

obtained from three independent experiments and tabulated in Table 332 Better

yields of 10-ethoxybenzo[h]quinoline were achieved using complex 23 (89) and 24

(83) employing SOCDTC compared to the literature procedure (51 mol 24 h 80)

However both the bimetallic complexes (25 and 26) demonstrated a lower catalytic

activity compared to their monometallic counterpart In order to achieve a quantitative

yield (gt90) of 10-isopropoxybenzo[h]quinoline it was necessary to increase the

reaction time particularly for 24 which required 24 hours for a 99 yield In addition

shorter times (2 - 4 hours) were all that was required to yield 92 - 99 of 10-

trifluoroethoxybenzo[h]quinoline using all dithiocarbamate catalysts tested Overall

this new approach offers milder and safer reaction conditions along with the same or

88

better catalytic activity in Reaction A using complexes 23 25 and 26 compared to the

literature procedure18 Only the catalytic activity of homoleptic complex 24 was found

to be affected when the transformation was performed at lower temperatures The

analysis of methoxylation of 8-methylquinoline was carried out in a similar manner

The percentage yield of product was found to be lower (lt 80) by employing SOCDTC

in comparison to the literature conditions (19 mol Pd(OAc)218 h 80)

Table 332 Summary of optimum catalytic activity results for Reactions A and B by dithiocarbamate

catalysts 23-26 (3 mol) Oxidant = PhI(OAc)2 T = 50 degC

Reaction R Catalyst Time

(h)

Yield

()

SD

A

Et

23 2 89 (20)

24 2 83 (10)

25 2 64 (21)

26 2 65 (35)

Pri

23 8 90 (14)

24 24 99 (00)

25 4 97 (12)

26 8 91 (25)

CH2CF3

23 4 92 (10)

24 4 99 (00)

25 2 99 (06)

26 2 95 (17)

B

Me

23 2 66 (02)

24 6 40 (02)

25 2 78 (02)

26 2 46 (44)

34 Palladium dithiooxamide catalysts

As demonstrated above transition metal catalysts are able to lower the activation

energy and allow the reaction to proceed faster and with lower energy requirements

However these metals are limited in supply and consequently very expensive The

dithiocarbamate palladium(II) complexes described above are typically generated

89

from palladium salts derived from mining which is also an environmentally-damaging

process These aspects have led to tremendous efforts to substitute these PGMs with

less expensive and more abundant materials for catalysis but few alternatives have

been found to be as effective and versatile as PGM metals

Thus a recovery process for PGMs is required to salvage the precious metals and

especially palladium from waste (secondary sources) to decrease the dependence

on the limited natural resources It would thus be ideal to identify a bidentate sulfur

ligand which is able to selectively recover palladium metal and then allow the complex

formed to be applied directly as a catalyst in C-H functionalization reactions without

any further purification For this purpose complexes 27 28 and 29 were prepared by

reaction of a bidentate dithiooxamide with palladium metal under mild conditions and

the resulting products were then tested to determine their catalytic activity

341 Initial catalytic screening

The activity of palladium(II) dithiooxamide complexes as potential catalysts for C-H

activation was tested using the benchmark reaction of methoxylation of

benzo[h]quinoline (Reaction A) The conversion to 10-methoxybenzo[h]quinoline was

achieved in 95 yield using Pd(OAc)2 (1 mol) as a catalyst in 22 hours at 100 degC

which confirmed the findings in the literature18 In order to establish whether such

forcing conditions were necessary a shorter reaction time (2 h) employing the same

protocol was explored using complex 27 Very surprisingly this gave a very good yield

of 87 indicating that the reaction was much more facile than the literature conditions

would suggest This significant finding prompted us also to investigate the effect of

temperature especially given the hazards caused by heating methanol at 100 degC in

the original protocol Keeping all the other parameters unchanged the temperature

was reduced to 50 degC causing the yield of the product to decrease to 67 with 27 as

the catalyst and to 33 when Pd(OAc)2 was used (Table 341) Thus optimised

conditions for different alkoxy functionalization were explored by tuning the catalyst

loading while maintaining the temperature at 50 degC

90

Table 341 Summary of initial catalytic screening results for Reaction A with ROH Oxidant = PhI(OAc)2 loading = 1 mol T = 50 and 100 degC

Reaction R Catalyst Pd

(mol)

Temperature

(degC)

Time

(h)

Yield

()

A

Me

Me

27 1 100

100

2 87

Pd(OAc)2 1 22 95

Me 27 1 50 2 67

Me Pd(OAc)2 1 50 2 33

342 Optimization of standard operating conditions for dithiooxamide

catalysts (SOCDTO)

Two variables (time and Pd loading) were manipulated while maintaining a

temperature of 50 degC in order to explore the catalytic performances of 27 for different

types of alkoxy functionalization Figure 341 provides the experimental data for the

methoxylation of benzo[h]quinoline at 50 degC It is apparent that 1 mol Pd loading

required longer reaction times to produce a near-quantitative yield of product This

finding suggests that as expected the decrease in temperature led to a decrease in

the rate of chemical reaction By doubling the palladium loading to 2 mol a

quantitative conversion of the product was obtained (99) in just 2 hours

Figure 341 Optimization of conditions for the methoxylation of benzo[h]quinoline Catalyst = 27 Oxidant = PhI(OAc)2 T = 50 degC

0

20

40

60

80

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

1 mol 2 mol

91

A similar observation was recorded for the catalytic reaction to produce 10-ethoxy

benzo[h]quinoline (Figure 342) Increasing the palladium loading increases the rate

of reaction allowing the reaction to reach completion in a shorter time In this

transformation an even shorter reaction time (1 hour) was able to produce 96 of the

product using 27 (2 mol) as the catalyst An additional hour of stirring seemed to

have little additional effect as the conversion rates for different palladium loadings

reached a plateau after 2 hours

Figure 342 Optimization of conditions for the ethoxylation of benzo[h]quinoline Catalyst = 27 Oxidant = PhI(OAc)2 T = 50 degC

When exploring the installation of more sterically-demanding alkoxy moieties product

conversions of 72 and 71 were reported in the literature18 for R = Pri (t = 27 h 33

mol Pd(OAc)2 T = 100 degC ) and R = CH2CF3 (t = 21 h 13 mol Pd(OAc)2 T = 100

degC) However similar results are readily achieved by complex 27 in only 1 and 2 hours

respectively employing a 2 mol palladium loading at 50 degC (Table 342) Overall

the activity of 27 as a catalyst for these reactions was very promising compared to the

literature protocol which required higher temperatures and longer reaction times

Thus the standard operating conditions for the dithiooxamide catalysts (SOCDTO) were

established as 2 mol 50 degC and 2 hours

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Time (hours)

1 mol 2 mol

92

Table 342 Reaction A catalysed by dithiooxamide complexes Oxidant = PhI(OAc)2 T = 50 degC Conversions determined by 1H NMR spectroscopy are an average of three independent experiments


(mol)

Time

(h)

Yield

()

SD

()

1

1 39 05

A

Pri

27

2 48 06

3 52 07

4 52 09

5 53 08

Pri

27

2

1 74 31

2 79 23

3 81 27

4 83 27

5 83 30

A

CF3CH2

27

2

1 49 05

2 72 09

3 85 11

4 92 00

5 96 05

It was then decided to explore the catalytic efficiency of the neutral species (28) and

the complex bearing the less expensive acyclic dithioxamide ligand (29)

Methoxylation of benzo[h]quinoline using 28 and 29 as catalysts reached more than

90 yield of the desired product under SOCDTO (Figure 343) A slight increase in

product conversion was observed when the reaction time was extended for another 1

or 2 hours

93

Figure 343 Methoxylation of benzo[h]quinoline Catalyst = 28 and 29 Oxidant = PhI(OAc)2

T = 50 degC

Once again a lower yield of product was recorded when using more sterically-

demanding reagents As can be seen in Figure 344 using catalyst 28 under the

SOCDTO a moderate yield of 10-isopropoxybenzo[h]quinoline (57) was obtained

compared to 10-ethoxybenzo[h]quinoline (88) which involves less steric hindrance

Extending the reaction time from 3 to 5 hours did not lead to a significant increase in

the product conversion

Figure 344 Ethoxy- and isopropyloxylation of benzo[h]quinoline Catalyst = 28 Oxidant = PhI(OAc)2 T = 50 degC

89

9899 99

85

92

9596

75

80

85

90

95

100

105

1 2 3 4

Yie

ld (

)

Time (hours)

Catalyst 28 Catalyst 29

40

50

60

70

80

90

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

EtOH iPrOH

94

The scope of the study was extended to the acetoxylation of benzo[h]quinoline

(Reaction C Figure 345) The reaction proceeded by mixing benzo[h]quinoline

complex 27 (1-2 mol) and PhI(OAc)2 in acetonitrile at 50 degC

Figure 345 Acetoxylation of benzo[h]quinoline

Figure 346 clearly indicates that a lower yield of product was obtained (lt 20) using

both 1 or 2 mol Pd loading for reaction times ranging from 1 to 5 h at 50 degC This

suggests that at a lower temperature a smaller proportion of molecules have enough

activation energy needed to react and generate the product This result led us to adopt

the literature18 protocol temperature (75 degC) for comparison Interestingly the reaction

using 2 mol of 27 produced a comparable yield (86) after just 9 hours of reaction

compared to the 12 hours reported by Sanford and co-workers employing Pd(OAc)2

Figure 346 Acetoxylation of benzo[h]quinoline Catalyst = 27 oxidant = PhI(OAc)2 T = 50 and 75 degC

0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10

Yie

ld (

)

Time (hours)

1 mol 50 degC 2 mol 50 degC 2 mol 75 degC

95

The ability of dithiooxamide complexes 28 and 29 to act as catalysts for the different

substrates was confirmed by a quantitative yield of 8-(methoxymethyl)quinoline using

SOCDTO (Table 343) This result far exceeds the literature value18 that showed only

80 conversion using 19 mol Pd(OAc)2 at 100 degC after 18 hours of reaction

Table 343 Reaction B catalysed by dithiooxamide complex 28 and 29 Oxidant = PhI(OAc)2 T = 50 degC


(mol)

Time

(h)

Yield

()

SD

()

2

1 53 11

B

OMe

28

2 95 05

3 100 05

4 100 00

5 100 00

B

OMe

29

2

1 54 20

2 89 08

3 99 02

4 100 00

5 100 00

343 Isolated yield of the products

A scaled-up reaction was carried out to support the validity of the 1H NMR integration

result Catalyst 27 was used on a larger scale methoxylation reaction of

benzo[h]quinoline employing SOCDTO A brown oil was collected after the removal of

the solvent by rotary evaporation A flash column with silica as the stationary phase

was set up to purify the mixture to yield 10-methoxybenzo[h]quinoline employing 32

vv ethyl acetate to n-hexane as an eluent A pale yellow solid was collected with 93

yield being in good agreement with that determined by 1H NMR analysis (99)

8-(Methoxymethyl)quinoline was prepared by reaction of 8-methylquinoline and 2

mol of complex 27 at 50 degC for 4 hours in methanol All the solvent was removed

96

under reduced pressure to yield an oily product This was dissolved in 91 vv hexane

and ethyl acetate and a flash column performed to gave a yellow oil in 98 yield

Again this isolated yield compares well with the 1H NMR spectroscopic integration

method (100)

35 Conclusion

The work in this chapter was inspired by two essential aspects of lsquogreen chemistryrsquo

namely the recovery of palladium from Three-Way Catalyst (TWC) waste and its reuse

as a homogeneous catalyst in organic synthesis without further modification of the

recovery product First it was demonstrated that sulfur ligands could be used to

support metal-mediated catalytic C-H activation This was then expanded to show that

palladium(II) complexes obtained from secondary sources (waste) using

dithioxamides (leaching agent) and iodine (oxidant source of counteranions) are

active homogeneous catalysts for the selective C-H activation reaction under mild

conditions Complexes 27 and 28 obtained from the recovery process of spent TWCs

were used directly as catalysts in the C-H activation of benzo[h]quinoline and 8-

methylquinoline Surprisingly both catalysts demonstrated a quantitative yield at

milder and safer conditions (50 degC 2 mol 1-3h) than those used in the literature

protocol (100 degC 1-5 mol 22-27 h) which employs commercially-available Pd(OAc)2

as a catalyst These results prompted us to employ the inexpensive acyclic ligand

Cy2DTO for the Pd recovery to form [Pd(Cy2DTO)2]I8 (29) which displays a slightly

lower (lt 90) catalytic activity than complexes 27 and 28 This breakthrough could

ultimately decrease the financial cost of synthesising palladium catalysts by using

secondary production material (TWC waste) instead of sources from often

environmentally-damaging mining (primary production) Thus these finding will

increase the value of the metal recovered from industrial waste and reduce the burden

on natural reserves as primary sources for scarce and expensive materials like PGMs

for catalytic applications

The other significant finding is the dithiocarbamate complex catalysed C-H activation

of benzo[h]quinoline and 8-methylquinoline with different alkoxy functionalities

Dithiocarbamates are versatile ligands but have little precedent in the support of

catalytic activity All dithiocarbamate complexes except 24 produced a quantitative

97

yield of product (gt 90) in the methoxylation of benzo[h]quinoline using SOCDTC

compared to the more forcing conditions used in the literature (100 degC 12 mol 22

h) The catalytic activity of complex 24 was found to be limited at 50 degC which might

be due to greater resistance to substitution of the two chelating DTC ligands compared

to the more labile phosphines present in the other complexes Installation of a variety

of functional groups (R = OEt OiPr and OCH2CF3) in the benzo[h]quinoline substrate

was successfully achieved albeit requiring extended reaction times compare to the

dithiooxamide compounds

98

36 References

1 A J Hunt A S Matharu A H King and J H Clark Green Chem 2015 17 1949ndash1950

2 M C F Steel Stud Surf Sci Catal 1991 71 105ndash114

3 K C Taylor in Catalysis Springer Berlin Heidelberg Berlin Heidelberg 1984 pp 119ndash170


5 J Moulijn A van Diepen and F Kapteijn Appl Catal A Gen 2001 212 3ndash16

6 T Tabata K Baba and H Kawashima Appl Catal B Environ 1995 7 19ndash32

7 B Stenbom G Smedler P Nilsson and S Lundgren in SAE Technical Paper 1990

8 H Shinjoh M Hatanaka Y Nagai T Tanabe N Takahashi T Yoshida and Y Miyake Top Catal 2009 52 1967ndash1971


10 C Hageluumlken J Lee-Shin A Carpentier and C Heron Recycling 2016 1 242ndash253

11 H Dong J Zhao J Chen Y Wu and B Li Int J Miner Process 2015 145 108ndash113


13 A Serpe F Artizzu M L Mercuri L Pilia and P Deplano Coord Chem Rev 2008 252 1200ndash1212



16 X Chen K M Engle D-H Wang and J-Q Yu Angew Chem Int Ed Engl 2009 48 5094ndash5115




99

20 R Colton M F Mackay and V Tedesco Inorganica 1993 207 227ndash232

21 E R Knight A R Cowley G Hogarth and J D E T Wilton-Ely Dalton Trans 2009 0 607ndash609

22 F Jian F Bei P Zhao X Wang H Fun and K Chinnakali J Coord Chem 2002 55 429ndash437

23 G Hogarth E-J C-R C R Rainford-Brent S E Kabir I Richards J D E T Wilton-Ely and Q Zhang Inorganica Chim Acta 2009 362 2020ndash2026



26 K Oliver A J P White G Hogarth and J D E T Wilton-Ely Dalton Trans 2011 40 5852ndash5864


28 G Hogarth in Transition Metal Dithiocarbamates 1978-2003 2005 pp 71ndash561

29 N Bricklebank S M Godfrey C A McAuliffe and R G Pritchard J Chem Soc Chem Commun 1994 0 695

100

4 Generation of homogeneous palladium catalysts from secondary sources

using simple ligands


In Chapter 3 selective metal leaching was combined with application in catalysis to

recover palladium from spent three-way catalysts (TWCs) and to apply the complexes

generated directly in homogeneous catalysis In doing so the energy-intensive step of

metal recovery (reduction from PdII to Pd0) can be avoided lowering the cost and the

environmental impact of producing an active catalyst and thus promoting the

sustainability of the recovery process

Among the ligands employed NNrsquo-dimethylperhydrodiazepine-23-dithione

[Me2dazdt] was recognised as an excellent ligand for the palladium leaching process

As an iodine adduct it can completely dissolve palladium in a highly selective manner

to form PdII complexes from the milled residue of catalytic converters in a single step

under mild aerobic conditions (80 degC) and in relatively short times compared to

conventional processes1 However the use of relatively expensive starting materials

and Lawessonrsquos reagent as a stoichiometric reagent for the addition of the sulfur

groups to the ligand ultimately reduces the economic and environmental benefits of

using this ligand in the recovery process This undermines to some extent the lsquogreenrsquo

credentials of the process and so other alternative ligands were explored in parallel

In order to overcome this limitation while still exploiting the superior leaching

properties of iodineiodide mixtures to extract palladium from spent TWCs a much

simpler cheaper and commercially available system was sought Contemporaneous

work by our collaborators at the University of Cagliari led by Dr Angela Serpe

demonstrated the impressive ability of organic triiodides OrgI3 where Org+ = 35-

bis(phenylamino)-12-dithiolylium [(PhHN)2DTL]+ 35-bis(morpholino)-12-12-

dithiolylium [Mo2DTL]+ tetrabutylammonium [TBA]+ and tetraphenylphosphonium

[Ph4P]+ in the selective dissolution of palladium from spent TWCs2

In order to explore the metal complexes generated by this system palladium metal

powder was used as a proxy for the milled TWC mixed-metal powder2 The use of

101

iodine in the presence of a simple tetrabutylammonium salt [TBA]I leads to the

dissolution of the palladium metal followed by precipitation of (TBA)2[Pd2I6]2 It was

proposed that this complex generated from this recovery process should be tested as

a potential homogeneous catalyst for the C-H oxidative functionalization reactions of

benzo[h]quinoline and 8-methylquinoline

In analogy to the work of Sanford and co-workers these palladium catalyst systems

should be able to functionalise C-H bonds in the benchmark substrates

(benzo[h]quinoline and 8-methylquinoline) in the presence of air with a broad scope

high efficiency selectivity and functional group tolerance requiring only nitrogen as a

directing atom345 These processes have a very high potential to be applied in organic

transformations for pharmaceutical applications including synthesis of natural

products andor biologically active molecules such as Paclitaxel (Taxol) Naproxen

and Singulair56

Besides C-H activation the complexes prepared will be tested for other Pd-catalysed

reactions namely C-C couplings which are even more widely used in organic

synthesis While the C-H activation described above has been proposed to be

catalysed by PdII species via PdIV or PdIIIPdIII intermediates7 C-C coupling usually

involves Pd0 and PdII intermediates The zerovalent active species are frequently

generated from PdII complexes such as [PdCl2(PPh3)2] This compound is widely used

for C-C couplings with the essential zerovalent intermediate being accessible under

the right reaction conditions

In this Chapter new synthesis routes to catalytically-active Pd(II) complexes are

proposed using simple ligand exchange reactions based on (TBA)2[Pd2I6] with

inexpensive phosphine ligands For example it was hypothesised that treatment of

(TBA)2[Pd2I6] with triphenylphosphine (PPh3) in acetone could lead to the formation of

[PdI2(PPh3)2] an analogue of [PdCl2(PPh3)2] which is widely used as a catalyst in

Suzuki and Sonogashira reactions Success in this approach would allow other

phosphine analogues such as 12-bis(diphenylphosphino)ethane (dppe) and 11-

bis(diphenylphosphino)ferrocene (dppf) to be used All the complexes generated from

102

ligand substitution reactions will be tested with different standard substrates for the

Suzuki-Miyaura cross-coupling reaction

The research described here presents the direct use of simple inexpensive palladium

recovery products in a wide range of important catalytic reactions The generation of

these catalytic species from (TBA)2[Pd2I6] and phosphine ligands will be explored to

improve further the advantages of using (TBA)2[Pd2I6] as a catalyst precursor

Reactions for which these complexes exhibit potential as catalysts will be further

optimised by varying the conditions including temperature time and catalyst loading

Optimised conditions reactions will be scaled up and the isolated yields recorded



1 Synthesise a bimetallic palladium complexes (TBA)2[Pd2I6] and used it as a

homogeneous catalyst in C-H functionalization reaction of benzo[h]quinoline to

10-alkoxy benzo[h]quinoline and 8-methylquinoline to 8-(methoxymethyl)- and

8-(acetoxymethyl) quinoline in the presence of the oxidant PhI(OAc)2

2 Extending the catalytic studies on the direct use of the phosphine-free recovery

compound (TBA)2[Pd2I6] as a catalyst in the carbon-carbon coupling reaction

3 Synthesise a range of PdI2(phosphine) complexes analogue via a simple ligand

exchange reaction and employed it as a homogeneous catalyst in a Suzuki-

Miyaura cross-coupling reaction of different standard substrates

42 Synthesis and characterisation of Pd(II) complexes derived from a

secondary source

A summary of the proposed palladium complexes to be synthesised and characterised

is provided in Figure 421 The metal recovery product (TBA)2[Pd2I6] (30) was itself

tested as potential homogeneous catalysts for the C-H functionalization and Suzuki-

Miyaura reaction A simple ligand substitution reaction between 30 and different

phosphines generates trans-[PdI2(PPh3)2] (31) [PdI2(dppe)] (32) and [PdI2(dppf)]

(33) which will be used as a catalyst in the Suzuki-Miyaura cross-coupling reaction

103

421 Synthesis and characterisation of palladium complexes

Following a modified literature protocol2 the reaction of palladium metal in powder

form with iodine and tetrabutylammonium iodide in acetone led to a dark solution from

which precipitated the black product (TBA)2[Pd2I6] (30) after continuous stirring for 2

hours All solvent was removed under reduced pressure and the product was re-

crystallised by slow diffusion of diethyl ether in a concentrated acetone solution of 30

to give an 86 final yield The infrared and UV-Vis analysis of 30 were in agreement

with those previously reported for this complex2

Figure 421 Proposed ligand substitution reactions

Complex 30 was then used as a starting point for ligand substitution reactions The

first transformation tested was the preparation of trans-[PdI2(PPh3)2] (31) by reaction

of 30 with triphenylphosphine in acetone for 2 hours to obtain a reddish-orange

precipitate (90 yield) The 31P1H NMR spectrum showed a new singlet peak

resonating at 128 ppm without any trace of free triphenylphosphine (-52 ppm) or

triphenylphosphine oxide (250 ppm) The 1H NMR spectra showed multiplets in the

104

aromatic region attributed to the protons in the triphenylphosphine The mass

spectroscopic analysis further confirmed the formulation of the complex In a similar

fashion complex 31 can be prepared by reaction of [PdI2(Me2dazdt)] (28) with

triphenylphosphine in acetone Similar spectroscopic data were obtained also for this

route An attempt to grow crystals of 31 by slow diffusion of diethyl ether into a

concentrated chloroform solution of the complex afforded deep red block crystals

suitable for analysis Preliminary analysis of the unit cell of single crystals of 31 by X-

ray crystallography confirmed the formulation as being the trans-[PdI2(PPh3)2]middotCHCl3

complex which has already been reported in the literature8

The trans geometry of 31 observed is noteworthy Generally nucleophilic substitution

reactions in square planar PdII complexes favour an associative mechanism9

However the unusual formation of trans-[PdI2(PPh3)2] product is likely to be due to the

steric implications caused by the presence of both bulky iodide and phosphine ligands

The large size of the incoming ligand (PPh3) forces the complex to accommodate the

iodide ligands in a trans disposition The possible mechanism for the formation of a

trans product can be hypothesised as ocurring by two different paths (a) through an

associative mechanism the incoming ligand (PPh3) attacks the metal either from

above or below the square planar system to form an intermediate (trigonal-bipyramidal

species) through the elimination of other ligands or (b) the lability of the ligands in the

solution permit the re-organization of the ligands to form a thermodynamically more

stable complex (Figure 422)

Figure 422 Proposed associative mechanism for ligand substitution reaction of the Me2dazdt ligand in [PdI2(Me2dazdt)] (28) by the PPh3 ligand

105

The focus of the studies on the ligand substitution of (TBA)2[Pd2I6] (30) was then

shifted from PPh3 to diphosphines starting with the 12-bis(diphenylphosphino)ethane

(dppe) ligand This ligand is known to be an effective ligand in catalytic reactions such

as the allylation of ketones10 The reaction of 30 with dppe in acetone at room

temperature for 2 hours provided [PdI2(dppe)] (32) as an orange precipitate A

dramatic change in the 31P1H NMR peak from -125 ppm (precursor) to 618 ppm

indicated the completion of the reaction 1H NMR analysis revealed signals for the

methylene bridge of dppe resonating at 233 ppm slightly downfield compared to

those of the precursor (209 ppm) along with a multiplet resonance in the aromatic

region which was attributed to the phenyl group In a separate experiment following a

similar procedure the reaction of [PdI2(Me2dazdt)] (28) with dppe in acetone solution

also formed complex 32 The spectroscopic data obtained agreed with those reported

above11

Complexes with ferrocenyl phosphine ligands are extensively used as catalysts for

alkene hydroformylation alkoxycarbonylation and Heck coupling reactions12 Thus 30

was treated with 11-bis(diphenylphosphino)ferrocene (dppf) in acetone at room

temperature affording the orange bimetallic complex [PdI2(dppf)] (33) The 31P1H

NMR spectrum of the complex showed a new singlet resonance at 242 ppm In the

1H NMR spectrum the two broad resonances observed at 417 and 437 ppm were

attributed to the ferrocenyl protons while the phenyl groups were found to resonate

further downfield in the aromatic region confirming the formation of the complex

All the compounds synthesised in this chapter are derived from the (TBA)2[Pd2I6]

complex (30) which can be obtained from the sustainable leaching of palladium from

a secondary source of palladium The catalytic ability of the complexes in either C-H

activation or Suzuki-Miyaura cross-coupling reactions are presented in the following

sections

43 C-H functionalisation reactions catalysed by (TBA)2[Pd2I6]

In the previous chapters the excellent catalytic activity of Pd(II) complexes bearing

dithiooxamide and dithiocarbamate ligands towards C-H functionalization reactions

has been demonstrated using milder and safer (50 degC) conditions13 compared to

literature protocols3 The palladium complex bearing Me2dazdt ligand showed the best

106

catalytic activity compared to the other catalysts tested However the ligand is

relatively expensive to prepare and requires the use of Lawessonrsquos reagent As an

alternative to these complexes compound 30 was synthesised from cheaper and safer

precursors and was tested as a potential catalyst for the oxidative C-H bond activation

benzo[h]quinoline (Figure 431)

Figure 431 Oxidative C-H Functionalisation reactions investigated

By employing a similar protocol13 benzo[h]quinoline (diacetoxy)iodobenzene

[PhI(OAc)2] and (TBA)2[Pd2I6] (30) were dissolved in the appropriate solvent Small

aliquots were removed and analysed by 1H NMR spectroscopy in order to determine

the product yields The alkoxybenzobenzo[h]quinoline product yield was obtained by

comparing the integration of resonances of H-2 (930 ppm) and H-10 protons (901

ppm) of benzo[h]quinoline with the diagnostic resonance of methoxy (CH3) ethoxy

(CH2CH3) and trifluoroethoxy (CH2CF3) groups which appeared at 419 163 and

445 and 474 ppm respectively in the alkoxy products In a similar fashion the yield

of 8-(methoxymethyl)quinoline was determined by comparing the integration of methyl

resonances (282 ppm) of 8-methylquinoline with the resonances of methylene (519

ppm) and methoxy group (357 ppm) in the product Three repeat experiments were

conducted and an average value calculated

431 Preliminary catalytic studies

Preliminary catalytic studies for the alkoxylation of benzo[h]quinoline catalysed by 30

were conducted by employing a standard literature protocol used in our earlier work13

(1-2 mol catalyst loading 100 degC 2h) The experiments consisted of dissolution of

the substrate PhI(OAc)2 and 30 in different alcohols to produce a variety of alkyl-aryl

ethers Table 431 shows that using 1 mol catalyst loading at 100 degC in methanol

107

and trifluoroethanol yields of 94 and 93 can be obtained respectively However

under the same conditions low conversions to 10-ethoxybenzo[h]quinoline (43) and

10-isopropoxybenzo[h]quinoline (52) were observed and these reactions required

a two-fold increase (2 mol) in catalyst loading to provide a better product yield This

finding indicates that 30 is a useful catalyst in the C-H functionalization of

benzo[h]quinoline at high temperatures even over short reaction times

Table 431 showing results for Reaction A using 30 as a catalyst (1 and 2 mol) Oxidant = PhI(OAc)2 solvent = MeOH EtOH iPrOH and CF3CH2OH and T = 100 degC

Reaction Pd loading R Time (h) Yield (SD)

A

1 mol

Me 2 94 ( 02)

Et 2 43 ( 02)

Pri 2 52 ( 47)

CH2CF3 2 93 ( 30)

2 mol

Me 2 99 ( 04)

EtOH 2 81 ( 33)

Pri 2 75 ( 40)

CH2CF3 2 99 ( 15)

Another interesting observation is the formation of a black precipitate at the bottom of

the reaction vials after 2 hours of reaction at 100 degC for all substrates except for the

trifluoroethanol reaction mixture This black precipitate was centrifuged at 6400 rpm

for 15 minutes and the supernatant removed The resulting black material was washed

with methanol (3 x 10 mL) followed by centrifugation until the washings were clear

The precipitate was dried under vacuum overnight Attempts to dissolve the black

precipitate using various solvents (MeOH EtOH acetone or toluene) proved

unsuccessful However the precipitate could be suspended in acetonitrile allowing

the preparation of samples for transmission electron microscopy (TEM) analysis

All the black precipitates collected from the C-H activation reactions of

benzo[h]quinoline in methanol ethanol and mixtures of iso-propanol were analysed by

TEM and revealed the formation of small nanoparticles (Figure 432) Average

108

diameters of 160 plusmn 05 nm (methanol) and 154 plusmn 03 nm (ethanol) were recorded

based on the measurement of over 50 nanoparticles The TEM analysis of the solid

obtained from the mixture of isopropanolacetic acid showed palladium nanoparticles

with an average size of 145 plusmn 06 nm The palladium nanoparticles formed during the

reaction could be influenced by the presence of the solvent which could help promote

the reduction of the PdII complex to Pd014

Figure 432 TEM images of palladium nanoparticles formed in A) MeOH B) EtOH C) iPrOH

It is not immediately clear why there is no formation of nanoparticles in the

trifluoroethanol reaction mixture A possible explanation might be due to the presence

of the electron-withdrawing fluorine groups in the solvent which stabilises the

palladium(II) complex effectively leading to no precipitate at high temperature (100

degC) even after performing the reaction for a week

While palladium nanoparticles catalyse Suzuki coupling reactions they are known to

be inactive in C-H oxidative functionalisation reactions as these transformations need

a Pd(II)-Pd(IV) manifold that is not available for nanoparticles Thus the presence of

these nanoparticles led us to re-assess the protocol used by Sanford3 which uses

Pd(OAc)2 as a catalyst in the C-H activation of benzo[h]quinoline Table 432 shows

the catalytic conditions and yield of substrates reported by Sanford and co-workers for

the methoxylation of benzo[h]quinoline The results clearly demonstrate that a

quantitative yield (95) of the product was obtained after 22 hours reaction at 100 degC

However shorter reaction times and milder conditions were not explored in this

original work

109

Table 432 Literature conditions3 and yields for the alkoxylation of benzo[h]quinoline using Pd(OAc)2

catalyst and PhI(OAc)2 as sacrificial oxidant at 100 degC

An initial assessment was conducted by treating benzo[h]quinoline

(diacetoxy)iodobenzene with 11 mol of [Pd(OAc)2] in MeOH at a lower temperature

(50 degC) over various timeframes (1 2 5 and 22 h) No black precipitate was observed

even after 22 hours under these conditions The solvent in the reaction mixture was

removed under reduced pressure and the residue was dissolved in CDCl3 for 1H NMR

analysis to calculate the product yield In Table 433 a clear trend of increase in yield

as the reaction is monitored for longer times can be seen However a satisfactory

conversion (87) is only achieved after 22 hours of reaction

Table 433 showing results for Reaction A using Pd(OAc)2 as a catalyst Oxidant = PhI(OAc)2 and T = 50 degC and 100 degC

Temperature (degC) Solvent Loading t (h) Yield

50

MeOH

11 Pd

1 34

2 39

5 73

22 87

100

MeOH

11 Pd

1 91

2 90

5 92

22 92

We further examined the effect of high temperature (100 degC) on the reaction and found

an excellent yield (91) of product had formed after just 1 hour of reaction It appears

that Sanford and co-workers did not explore shorter reaction times but it seems that

no significant improvement in product yield is observed on extending the reaction time

Notably the formation of a black precipitate was always observed after 22 hours of

Reaction Solvent [Pd] (mol) Time (h) Yield ()

A MeOH 11 22 95

110

reaction This solid was isolated and analysed by TEM (Figure 433) The images

show the formation of Pd nanoparticles with an average diameter of 257 plusmn 11 nm

(based on 50 nanoparticles) The findings corroborate the suggestion by Wilkinson

and co-workers15 that Pd(OAc)2 dissolved in alcohols and heated decomposes to

palladium metal The formation of palladium nanoparticles was a little unexpected for

phosphine-free conditions as the formation of palladium nanoparticles is often

associated with the oxidation of any phosphine present16

Figure 433 TEM images of Pd nanoparticles formed employing Sanfordrsquos conditions (22 h reaction at 100 degC)

Further experiments were carried out to investigate the cause of the formation of the

palladium nanoparticles using the standard literature protocol for C-H

functionalization Three separate control experiments were conducted using Sanfordrsquos

protocol (100 degC 22 h 11 mol of Pd(OAc)2)3 In the first control experiment

benzo[h]quinoline (the substrate) was treated with Pd(OAc)2 in methanol to produce a

dark brown solution without the formation of any black precipitate In the second

control experiment Pd(OAc)2 was treated with PhI(OAc)2 (the sacrificial oxidant) in

methanol producing a black precipitate after completion of the reaction This

precipitate was analysed by TEM to reveal the formation of very small nanoparticles

with an average diameter of 116 plusmn 03 nm (Figure 434)

Figure 434 TEM images of palladium nanoparticles formed after Pd(OAc)2 was treated with the sacrificial oxidant PhI(OAc)2 in methanol

111

The final control experiment was conducted by heating the catalyst Pd(OAc)2 alone in

methanol at 100 degC for 22 hours Palladium nanoparticles were again obtained as

confirmed by the TEM images in Figure 435 The average diameter of the

nanoparticles was 146 plusmn 05 nm based on over 50 nanoparticles These findings

are corroborated by the observations of Reetz and Westermann that Pd(OAc)2 is

reduced on heating at 100 degC after 3 hours in a polar propylene carbonate solvent

system to form palladium colloidal nanoparticles with an average diameter of 8-10

nm17

Figure 435 TEM images of Pd nanoparticles resulting from heating Pd(OAc)2 in methanol at 100 degC for 22 hours

In summary this proved that Pd(OAc)2 can be reduced to palladium nanoparticles in

the presence of a sacrificial oxidant in an alcohol solvent at high temperature14 There

have been no previous reports of the potential for the sacrificial oxidant to promote the

reduction of palladium complexes However heating Pd(OAc)2 in alcohol solution is

known to lead to nanoparticle formation15

In general C-H functionalization is believed to proceed via a catalytic cycle involving

PdIIPdIV species18 Thus further investigation was required to prove that the C-H

functionalization of benzo[h]quinoline is not catalysed by zerovalent palladium

nanoparticles Evidence for this was obtained by heating Pd(OAc)2 in methanol at

100 degC for 2 hours forming nanoparticles as described above Then

benzo[h]quinoline and PhI(OAc)2 were added directly to the reaction mixture and the

heating continued for another 22 hours At the end of the reaction a black precipitate

remained but no conversion of benzo[h]quinoline to any products was detected

Therefore it can be assumed that the methoxylation of benzo[h]quinoline using

the Sanford literature protocol is due to the fraction of Pd(OAc)2 that survives

112

the reduction to nanoparticles in the first few minutes or hours of the reaction

These findings also provide some support for the conceptual premise that the

C-H functionalization can be conducted under milder conditions than those

previously proposed in the literature

432 C-H functionalization of benzo[h]quinoline employing (TBA)2[Pd2I6] as a

catalyst

In the previous section it was shown that 10-methoxybenzo[h]quinoline could be

successfully formed from benzo[h]quinolone using (TBA)2[Pd2I6] or Pd(OAc)2 as a

catalyst in methanol However both catalytic systems showed the reduction of the

Pd(II) to Pd(0) at high temperatures This result prompted us to employ milder reaction

conditions using a lower temperature (50 degC) to explore functionalisation with

different alcohols and to vary the catalyst loading (1-2 mol )

Initially the reaction of 1 mol (TBA)2[Pd2I6] benzo[h]quinoline and [PhI(OAc)2] was

investigated in different alcohols at 50 degC Figure 436 shows a significant increase in

10-methoxybenzo[h]quinoline and 10-trifluoroethoxybenzo[h]quinoline yield over

extended reaction times Excellent yields (gt 90) of both products were obtained after

24 hours of reaction Meanwhile moderate yields (lt 50) were obtained for the

reactions employing ethanol and a mixture of isopropanol and acetic acid as solvents

These findings might be linked to the steric features of the reagent used For example

methanol has a higher polarity and less steric bulk than ethanol which could result in

higher product yield

113

Figure 436 Summary of catalytic results for Reaction A Catalyst = 30 (1 mol) oxidant = PhI(OAc)2 T = 50 degC

A different set of conditions was then tested with only a single variable being changed

To start the catalyst loading was doubled Data in Figure 437 show how the increase

of the catalyst loading (to 2 mol) dramatically enhances the yields of the desired

products (gt 95) allowing shorter reaction times (2 h) to be used The exception to

this was for 10-isopropoxybenzo[h]quinoline (68) which still showed a steady

increase in conversion to 10-isopropoxybenzo[h]quinoline (82) after 24 hours

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25

Yiel

d (

)

Time (hours)

MeOH EtOH PriOHAcOH CF₃CH₂OH

114


Based on these catalytic experiments the standard operating conditions (SOCPd2I6)

were set to 2 mol catalyst loading at 50 degC for 2 hours Under these conditions

catalyst 30 successfully functionalised benzo[h]quinoline with various functional

groups (OMe OEt O-iPr and OCH2CH3) at the C-10 position in essentially

quantitative yield (gt 95) with the exception of 10-isopropoxybenzo[h]quinoline

An experiment to determine the isolated yield for the methoxylation of

benzo[h]quinoline was conducted employing SOCPd2I6 A brown oil was collected after

removal of all solvent by rotary evaporation A flash column was used to purify the

mixture to yield 10-methoxybenzo[h]quinoline employing 32 vv ethyl acetate to n-

hexane as an eluent A pale-yellow solid was isolated 97 which was in agreement

with the conversion determined by the 1H NMR integration method (98)

433 C-H functionalisation of 8-methylquinoline

Encouraged by the successful results obtained for the alkoxylation of

benzo[h]quinoline the catalytic reaction was extended to the synthesis of

methoxymethyl- and acetoxymethylquinoline The transformation proposed is the

0

20

40

60

80

100

120

0 5 10 15 20 25 30

Yiel

d (

)

Time (hours)


115

selective installation of OMe (Figure 438 Reaction B) or OAc (Figure 438 Reaction

C) groups at the methyl position of the 8-methylquinoline

Figure 438 C-H Functionalization of 8-methylquinoline

In order to investigate Reaction B a methanolic solution of 8-methylquinoline

PhI(OAc)2 and 30 (1-2 mol) were stirred and heated at high temperature (100 degC) in

a reaction vial for 2 hours As shown in Table 434 a good yield of 8-

(methoxymethyl)quinoline (gt 80) was obtained with a slight difference (7) in

percentage yield when the catalyst loading was varied As expected heating the Pd(II)

complex in an alcohol solvent promoted the reduction to Pd(0) nanoparticles in the

form of a black precipitate at the bottom of the vials after completion of the reactions

Table 434 Catalytic results for Reaction B Catalyst = 30 Oxidant = PhI(OAc)2 and T = 100 degC

Reaction R Pd loading Time (h) Yield () (SD)

B Me 1 mol 2 80 (02)

2 mol 2 87 (16)

Continuing our efforts to develop greener synthetic pathways and increasing the

efficiency of the desired C-H functionalizations an energy saving approach was

adopted by lowering the temperature of the reactions Surprisingly the reaction of 8-

(methoxymethyl)quinoline with 1 mol of catalyst PhI(OAc)2 in methanol at 50 degC for

2 hours provided an even better conversion to 8-(methoxymethyl)quinoline (gt 96)

compared to the yield obtained at a 100 degC (Table 435) This result is comparable

116

with the performance of the catalyst [PdI2(Me2dazdt)] (28) in the methoxylation of 8-

methylquinoline which gave 95 yield under the same reaction set up Moreover it

should be noted that this procedure showed a far better yield in a shorter reaction time

(2 h) at a lower temperature (50 degC) compared to the work by Sanford and co-workers3

(80 yield 19 mol Pd(OAc)2 100degC 18 h) Doubling the catalyst loading under the

same reaction conditions provided complete conversion to the product (99)

The lower conversion at a higher temperature may be explained by the fact that the

palladium nanoparticles (formed at higher temperatures) agglomerate to form black

sediment that undermines the catalytic performance19 In conclusion the optimum

reaction conditions for the methoxylation of 8-methylquinoline were set at 1 mol

catalyst loading 2 hours of reaction at 50 degC 1H NMR analysis of the percentage yield

was verified by conducting a large-scale catalytic reaction to estimate the isolated

yield 8-methylquinoline (1275 mg) PhI(OAc)2 (3099 mg) and 1 mol of 30 were

mixed in methanol and stirred for 2 hours at 50 degC The solvent was removed under

reduced pressure and the resultant oil was dissolved in a mixture of hexane and ethyl

acetate (91 vv) and purified using a simple flash column to provide 14520 mg (94)

of 8-(methoxymethyl)quinoline as a yellow oil This result compared well with the yield

of 96 determined by the 1H NMR spectroscopic method

Table 435 Catalytic activity results for Reaction B Catalyst = 30 Oxidant = PhI(OAc)2 and T = 50 degC

Reaction Solvent Loading t (h) Yield SD

B

MeOH

1 mol

2 96 ( 02)

4 94 ( 17)

6 96 ( 03)

24 95 (12)

B

MeOH

2 mol

2 99 (06)

4 99 (04)

6 99 (04)

24 99 (05)

The acetoxylation of 8-methylquinoline was conducted by dissolving the substrate

PhI(OAc)2 and 30 in acetonitrile By shortening the reaction time to 2 hours and kept

117

all the parameter employed by Sanford3 unchanged (1 mol catalyst 100 degC) only

61 product yield was obtained compared to 88 (22 h) reported in the literature By

doubling the catalyst amount a quantitative yield (83) of 8-(acetoxymethyl)quinoline

was recorded which is indicated the scope of catalyst (Table 436)

Table 436 Catalytic activity results for Reaction C Catalyst = 30 Oxidant = PhI(OAc)2 and T = 100 degC

Reaction Solvent Pd loading Time (h) Yield SD

C AcOH 1 mol 2 61 ( 30)

2 mol 2 83 ( 40)

The effect of lowering the temperature to 50 degC was investigated and revealed

moderate performances of 30 compared to the reactions performed at higher

temperature (100 degC) For instance 1 mol of the catalyst at 100 degC gave a 61

product yield in 2 hours a result that can only be achieved after 6 hours at 50 degC

Furthermore it was found that the high yield of 8-(acetoxymethyl)quinoline (85)

afforded by the model reaction can only be achieved in 24 hours using 30 (2 mol)

as a catalyst (Table 437) A possible explanation of these findings might be due to

the presence of additional benzylic hydrogen atoms in the substrate This possibly

prevents further C-H functionalization of the product due to the steric hindrance at the

more substituted benzylic position3



C

AcOH

1 mol

2 44 ( 28)

4 55 ( 06)

6 62 ( 25)

24 71 ( 16)

C

AcOH

2 mol

2 71 ( 78)

4 71 ( 21)

6 72 ( 13)

24 85 ( 38)

118


It was then attempted to extend the scope of the studies to the methoxylation of

different substrates such as benzylamine (A) N-Benzylmethylamine (B) and 2-

methylphenol (C) The catalytic reactions were conducted by treating the relevant

substrate in the presence of PhI(OAc)2 and 30 in a methanolic solution (1-2 mol

catalyst 2 - 24hr 50 - 100 degC) However none of the anticipated products (2-

methoxybenzylamine 2-methoxy-N-methylbenzylamine or 2-methoxymethyl-phenol)

was detected (Figure 439) This is likely to be due to a failure to form the palladacycle

under these conditions

Figure 439 Unsuccessful C-H functionalization reactions


The success of the C-H activation reactions prompted us to employ (TBA)2[Pd2I6] (30)

in other palladium-catalysed reactions such as the Suzuki-Miyaura reaction This

reaction involves the cross-coupling of aryl-halides with aryl- or vinyl-boronic acids in

the presence of a palladium catalyst and a base (Equation 3)20 The commercial

palladium(II) catalysts such as Pd(OAc)2 21

and [PdCl2(PPh3)2]22 have proved to be

119

very effective in forming the required carbon-carbon bond through the interconversion

of Pd0 and PdII intermediates Generally the in situ reduction of Pd(II) to Pd(0) can be

accomplished by the addition of phosphine ligands (phosphine-assisted)2223 Under

phosphine-free reactions the palladium(II) reduction has been reported in the

presence of olefins2425 amine bases26 solvents27 or tetrabutylammonium salts28

Equation 3 Generic scheme for the Suzuki-Miyaura cross-coupling reaction (R1 and R2 aryl vinyl X Br Cl I Y OH O-R)

As mentioned previously (Section 42) the ligand exchange reaction of 30 with

phosphine ligands (PPh3 dppe dppf) leads to the formation of the Pd(II) complexes

[PdI2(PPh3)2] (31) [PdI2(dppe)] (32) and [PdI2(dppf)] (33) which are closely related to

[PdCl2(PPh3)2] which is known as a reliable air-stable precursor to the zerovalent

palladium active species29 Thus these complexes offer a wide selection of potential

recovery-derived catalysts to be tested in the Suzuki-Miyaura cross-coupling reaction

In this chapter phosphine-modified (31 32 and 33) and phosphine-free (30)

complexes are investigated in the Suzuki-Miyaura reaction If successful this would

be significant in showing the direct use of a simple inexpensive palladium recovery

product in an industrially important catalytic reaction

441 Catalysis reaction set up

The substrates chosen for the Suzuki-Miyaura cross-coupling reaction are aryl halides

and phenylboronic acid This combination is the most commonly used for the

production of biaryls as it uses (i) mild reaction conditions (ii) commercially available

stable and low toxicity boronic acid compounds and (iii) allows an extensive choice of

substrates with numerous functional groups30 The reactivity of the aryl halide depends

on the nature of the halides I gt Br gt Cl Thus the substrates to be tested will be

focused on aryl iodide (4-iodoanisole) and aryl bromide (4-bromoanisole 4-

bromotoluene and 4-bromonitrobenzene) compounds The most common and efficient

base is K2CO3 and this will be employed to produce hydroxides which promote the

formation of the tetrahedral boronate anion required for the transmetallation step31

120

The solvent is a significant component of the reaction because it must be able to

dissolve the reactants and the base Since our research approach has been to focus

on performing reactions under green conditions the solvent chosen was ethanol and

the temperature of the reaction was set below the boiling point of the solvent (75 degC)

to minimise the potential dangers related to pressure build-up in the vial and to

decrease the energy consumption Other parameters such as the duration of the

catalytic test (30-120 min) and catalyst loading (05 mol) were optimised to

determine standard operating conditions for the proposed Suzuki-Miyaura cross-

coupling reaction

The reaction was conducted with a slight modification of the literature protocol32 In

general aryl halides phenylboronic acid potassium carbonate and the selected

palladium catalysts were mixed in a vial containing ethanol The reaction mixture was

heated and vigorously stirred and the progress was monitored by 1H NMR

spectroscopy After the completion of the reaction the biphenyl product was separated

by filtration and the reaction mixture was extracted with water and dichloromethane

The organic layer was dried over magnesium sulfate and then evaporated under

reduced pressure The products can be purified by flash column chromatography

using ethyl acetate-n-hexane (140) if necessary

The biphenyl product yields were determined using the 1H NMR integration method

For the reactions of 4-bromoanisole and 4-iodoanisole the integration of their methyl

resonances (378 ppm for both) was compared to those of the diagnostic resonance

of the methoxy moiety (386 ppm)33 in the 4-methoxybiphenyl product The yield of 4-

methylbiphenyl was determined by comparing the integration of the methyl

resonances of 4-bromotoulene (230 ppm) with the resonances of the methyl group

(238 ppm)34 in the product Finally the comparison of phenyl resonances of 1-bromo-

4-nitrobenzene (813 ppm) and 4-nitrobiphenyl (828 ppm)35 determined the yields of

the last reaction Three repeat experiments were conducted to give an average

reading

121


4421 Coupling of aryl iodides with phenylboronic acid

The first cross-coupling transformation studied was the coupling of 4-iodoanisole with

phenylboronic acid using phosphine-modified complexes in the presence of K2CO3 as

a base at 75 degC (Figure 441) The reaction was stirred for a pre-determined amount

of time (30 60 and 90 min) and the white precipitate of 4-methoxybiphenyl produced

was dissolved with the appropriate amount of deuterated chloroform and analysed by

1H NMR spectroscopy36

The choice of aryl iodide as substrate was due to iodides being the best halide leaving

group (iodide gt bromide gt chloride)37 It was decided to focus attention on the use of

trans-[PdI2(PPh3)2] (31) [PdI2(dppf)] (32) and [PdI2(dppe)] (33) complexes derived via

ligand exchange reactions as potential homogeneous catalysts for carbon-carbon

coupling reactions

Figure 441 Coupling of 4-iodoanisole with phenylboronic acid

From the results in Table 441 it can be seen that 05 mol of catalyst loading can

successfully be used to convert the reactants to the product in high yields (gt 90)

within 60 min in ethanol at 75 degC There is limited literature on [PdI2(phosphine)]

complexes in Suzuki-Miyaura cross-coupling reactions As reported previously38

trans-[PdI2(PPh3)2] is actually generated as a minor product from the in situ reaction

of [Pd(PPh3)4] with 4-iodotoluene phenylboronic acid and Na2CO3 in a mixture of

THFH2O Using 05 mol trans-[PdI2(PPh3)2] in the presence of excess phosphine

only generated 46 of product from the reaction of 4-iodotoluene with phenylboronic

acid in DMF solution This finding might relate to the inability of the palladium iodide

intermediate to efficiently enter the catalytic cycle in the presence of excess PPh338

122

Table 441 Suzuki-Miyaura cross-coupling reaction of 4-iodoanisole with phenylboronic acid catalysed by the different catalysts

Catalyst Pd

loadings

(mol )

Yield ()

60 min 90 min 120 min

[PdI2(PPh3)2] (31)

05

945 plusmn 12 955 plusmn 15 955 plusmn 16

[PdI2(dppf)] (32) 988 plusmn 08 975 plusmn 11 985 plusmn 09

[PdI2(dppe)] (33) 910 plusmn 56 878 plusmn 21 905 plusmn 10

As far as we are aware there is no literature reporting the use of [PdI2(dppf)] (32) and

[PdI2(dppe)] (33) as catalysts in the Suzuki-Miyaura reaction However the chloride

analogue [PdCl2(dppf)] was reported to effectively catalyse the preparation of aryl

boronic esters from aryl halides38 Naghipour and co-workers reported that

[PdBr2(dppe)] was an effective catalyst for the C-C coupling of 4-iodoanisole with

phenylboronic acid in the presence of polyethene glycol (PEG) as a solvent with 85

of product obtained after 75 min of reaction at 90 degC36

To offer a more in-depth comparison regarding catalytic activity the commonly-used

phosphine-based catalyst [PdCl2(PPh3)2] was employed to benchmark the coupling

of 4-iodoanisole with phenylboronic acid under the same reaction conditions (05 mol

catalyst loading 30 and 60 min 75 degC) in ethanol The formation of a Pd(0) complex

by reduction of [PdCl2(PPh3)2] can be achieved on addition of a base to form

[PdCl(OH)(PPh3)2] as established by Grushin and Alper39 The results show 91 and

95 yields of 4-methoxybiphenyl after 30 and 60 min of reaction respectively As a

comparison to [PdCl2(PPh3)2] [PdI2(PPh3)2] (31) offers very similar catalytic activity in

the transformation whereas slightly lower and higher conversions were obtained for

[PdI2(dppe)] (33) and [PdI2(dppf)] (32) within 60 minutes Generally the phosphine-

based palladium catalyst tested successfully converted 4-iodoanisole to 4-

methoxybiphenyl in a high yield

Encouraged by these results it was decided to focus attention on the direct use of the

phosphine-free recovery compound (TBA)2[Pd2I6] (30) as a catalyst in the carbon-

carbon coupling reaction Initially the catalytic activity of 30 towards the cross-coupling

reaction of 4-iodoanisole with phenylboronic acid was investigated using a 1 mol

123

catalyst loading in a phosphine-free environment It was found that the coupled

product (4-methoxybiphenyl) was obtained in a quantitative 1H NMR spectroscopic

yield (99) after 60 min This result suggests that the solvent or tetrabutylammonium

salts are able to generate the required zerovalent palladium species in the absence of

phosphine No nanoparticles were observed under the conditions tested

Encouraged by this result the reaction was optimised regarding catalyst loading and

reaction temperature By lowering the loading of 30 to 05 mol and using shorter

reaction time (30 min) without changing other parameters a quantitative yield (99)

of the desired product was obtained A similar yield of 4-methoxybiphenyl was

observed when the reaction time was prolonged for a further 30 min (Figure 442) As

a comparison to [PdCl2(PPh3)2] 30 offers a slightly higher catalytic activity in the

transformation which might relate to the presence of tetrabutylammonium iodide

(TBAI) in the reaction mixture that acts as a phase transfer agent to facilitate the

reaction This hypothesis was supported by a reports of TBAI40 tetrabutylammonium

bromide (TBAB)414243 and tetrabutylammonium fluoride (TBAF)40 being used as

phase transfer agents to enhance the yield of biaryl products in Suzuki Miyaura cross-

coupling reactions

Figure 442 Cross-coupling reaction of 4-iodoanisole with phenylboronic acid

A large-scale cross-coupling reaction was conducted to prove the formation of the

desired product and to validate the 1H NMR integration method In a reaction vessel

80

85

90

95

100

105

(TBA)₂[Pd₂I₆] [PdCI₂(PPh₃)₂]

Yiel

d (

)

Catalysts

30 min 60 min

124

4-iodoanisole phenylboronic acid 30 and K2CO3 in ethanol were heated (75 degC) and

stirred for 30 min The white precipitate obtained was purified by flash column

chromatography using ethyl acetate and n-hexane (140) to yield 95 (175 mg) of 4-

methoxybiphenyl a slightly lower value than the yield obtained by 1H NMR integration

(99) probably due to human error during the purification process In conclusion the

use of 30 in the coupling of 4-iodoanisole with phenylboronic acid has several

advantages including a simple and environmentally (phosphine-free) procedure short

reaction time (30 min) excellent yield (99) and mild conditions (75degC - below the

boiling point of ethanol)

4422 Coupling of aryl bromides with phenylboronic acid

The scope of the investigation was broadened by examining the coupling reaction of

an aryl-bromide (4-bromoanisole) with phenylboronic acid using the same approach

(05 mol catalyst loading 30 60 90 min 75 degC) in ethanol (Figure 443) The

phosphine-free approach was employed using 30 as a catalyst in the presence of

K2CO3 in ethanol

Figure 443 Coupling of 4-bromoanisole with phenylboronic acid

As shown in Figure 444 using 05 mol of 30 a near-quantitative yield (96 ) of 4-

methoxybiphenyl was observed after 30 min A slight increase in yield of the product

was obtained as the reaction time was extended for another 60 min A comparable

catalytic activity in the same coupling reaction was obtained using [PdCl2(PPh3)2]

without the presence of excess triphenylphosphine Although phosphine ligands can

stabilise palladium and enhance the catalytic activity of C-C coupling reactions the

simplest and cheapest palladium catalyst is still the phosphine-free approach17 Thus

the fact that 30 is obtained directly from the palladium recovery process could offer a

significant advantage over commercially-available complexes such as [PdCl2(PPh3)2]

125

In addition the absence of phosphine contaminants makes the proposed protocol

even more advantageous

The reactivity of trans-[PdI2(PPh3)2] (31) [PdI2(dppe)] (32) and [PdI2(dppf)] (33) was

examined towards the coupling reaction of an aryl bromide (4-bromoanisole) with

phenylboronic acid in ethanol Using the same approach [PdI2(dppf)] (33) gave a

slightly lower yield (93) compared to phosphine-free approach (98) after 90 min of

reaction Good (78) and moderate (55) yields of the product were observed by

employing 31 and 32 as a catalyst after 90 min of reaction (Figure 445) A similar

pattern of catalytic data was observed after 120 and 150 min It seems that the less

reactive aryl bromide (compared to aryl iodides) affects the catalytic performance of

catalysts 31 and 32 substantially This finding was supported by the literature that

reports low (28) and very poor (2) yields in the reaction of aryl bromides with

phenylboronic acid when catalysed by Pd(OAc)2 in the presence of excess dppf and

dppe respectively in a mixture of propan-1-ol and water38

Figure 444 Cross-coupling reaction of 4-bromoanisole with phenylboronic acid

The large-scale cross-coupling of 4-bromoanisole (181 mg) with phenylboronic acid

(122 mg) was carried out Using 05 mol of 30 in the presence of K2CO3 as a base

the reaction was heated (75 degC) and stirred in ethanol for 30 min The white precipitate

obtained after removal of solvent under reduced pressure was purified using flash

80

85

90

95

100

30 60 90

Yie

ld (

)

Time (min)

(TBA)₂[Pd₂I₆] (30) [PdCl₂(PPh₃)₂]

126

column chromatography to yield 92 of 4-methoxybiphenyl a slightly lower yield

compared with the 1H NMR integration yield (96)

Figure 445 Comparison of various catalysts performance in a cross-coupling reaction of 4-bromoanisole with phenylboronic acid

4423 Effect of electron-donating and withdrawing substituents on the reaction

of aryl bromides with phenylboronic acid

The next experiments were devoted to investigating the effect of aryl bromides bearing

electron-donating (4-bromotoluene) or electron-withdrawing (4-bromonitrobenzene)

groups in a cross-coupling reaction with phenylboronic acid to form the desired biaryl

products employing the same protocol used previously (05 mol catalyst loading 30-

120 min 75 degC) The bimetallic palladium system (30) was indeed very efficient toward

these Suzuki coupling reactions and displayed remarkable yield of products (gt 97)

for both electron-donating and electron-withdrawing substituents after only 30 min

Similar catalytic activity was observed for [PdCl2(PPh3)2] which gave yields of 98

and 99 for 4-methoxybiphenyl and 4-nitrobiphenyl respectively after 60 min (Table

442) This result indicated that the electronic properties of the functional groups on

the benzene ring have a limited impact on the catalytic activity of 30

0

10

20

30

40

50

60

70

80

90

100

90 120 150

Pro

du

ct y

ield

(

)

Time (min)

(TBA)₂[Pd₂I₆] [PdI₂(PPh₃)] [PdI₂(dppf)] [PdI₂(dppe)]

127

Table 442 Cross-coupling reaction of aryl bromides with phenylboronic acid performed in ethanol catalysed by (TBA)2[Pd2I6] and PdCl2(PPh3)2

Aryl Halides Product Catalysts Timemin Yield ()

(TBA)2[Pd2I6] 30 974 plusmn 01

60 968 plusmn 04

[PdCl2(PPh3)2] 30 983 plusmn 02

60 973 plusmn 15


60 996 plusmn 01


60 995 plusmn 01

The catalytic activity of 31 32 and 33 towards the coupling reaction between 4-

bromotoulene and phenylboronic acid was then explored The yields of the product (4-

methoxybiphenyl) for the different catalysts are shown in Figure 446 Using 05 mol

catalyst loading a slightly lower yield of the product from the reactions with phosphine-

based catalysts was observed compared to the phosphine-free system (30) after 60

min of reaction This might be explained by the presence of the electron-donating

group on the benzene ring leading to a slower oxidative addition step in the reaction44

Figure 446 Comparison of catalyst performance in the cross-coupling reaction of 4-bromotoulene with phenylboronic acid

0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)

(TBA)₂[Pd₂I₆] [PdI₂(PPh₃)₂] [PdI₂(dppf)] [PdI₂(dppe)]

128

Finally the coupling reaction between 4-bromonitrobenzene (electron withdrawing)

with phenylboronic acid was investigated Surprisingly the 4-nitrobiphenyl product

was obtained in quantitative yield (gt 99) for all the catalysts in the study over a short

reaction time (30 min) This finding supports the suggestion that the electron

withdrawing group facilitates the rate-limiting oxidative addition step which leads to a

higher yield of the desired biaryl product45 In general the palladium-based phosphine

catalysts showed decent activity for substrates with electron-withdrawing groups

compared to electron-donating groups

Figure 447 Comparison of catalyst performance in a cross-coupling reaction of 4-bromonitrobenzene with phenylboronic acid

45 Conclusion

This chapter describes an alternative way to recover Pd metals from TWC waste using

iodine with a simpler cheaper and commercially available tetrabutylammonium iodide

This compares well to the use of the Me2dazdtmiddot2I2 system which requires relatively

expensive starting materials to prepare The bimetallic palladium complex

(TBA)2[Pd2I6] (30) obtained from the leaching process was directly used as a

homogeneous catalyst in the C-H activation of benzo[h]quinoline and 8-

methylquinoline A quantitative yield in the alkoxylation of benzo[h]quinoline and

methoxy- and acetoxylation of 8-methylquinoline was obtained at low temperatures

(50 degC) It was also observed that heating (TBA)2[Pd2I6] at 100 degC in alcoholic solvents

leads to the reduction of Pd(II) to Pd(0) and the formation of nanoparticles Non-

0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


129

nanoparticulate zerovalent palladium species were generated from the same

precursor leading to a high catalytic activity in the Suzuki-Miyaura cross-coupling

reaction between aryl halides and phenylboronic acid to produce biaryl compounds in

excellent yield

The development of a new synthetic route to synthesis Pd(II) complexes via simple

ligand exchange reactions of (TBA)2[Pd2I6] with inexpensive phosphine ligands such

as PPh3 dppe and dppf allowed the generation of trans-[PdI2(PPh3)2] [PdI2(dppe)]

and [PdI2(dppf)2] complexes respectively These complexes showed moderate to high

catalytic activity in various standard Suzuki-Miyaura cross-coupling reactions In

summary (TBA)2[Pd2I6] can be recognised as a simple versatile and multifunctional

compound obtained from secondary sources which shows high activity in the

homogeneous palladium-based catalysis of C-H functionalization and Suzuki-Miyaura

cross-coupling reactions

130

46 References




4 Lopa V Desai A Kami L Hull and M S Sanford J Am Chem Soc 2004 126 9542ndash9543



7 D C Powers and T Ritter Nat Chem 2009 1 302

8 I D PGJones CSD Commun Priv Commun CCDC refcode EZOSUH

9 F Basolo in Mechanism of Inorganic Reactions 1965 pp 81ndash106

10 J Tsuji I Minami and I Shimizu Tetrahedron Lett 1983 24 4713ndash4714

11 S Aizawa A Majumder D Maeda and A Kitamura Chem Lett 2009 38 18ndash19

12 R S Chauhan D B Cordes A M Z Slawin S Yadav and C Dash Inorganica Chim Acta 2018 478 125ndash129


14 M T Reetz G Lohmer and R Schwickardi Angew Chemie Int Ed 1998 37 481ndash483

15 T A Stephenson S M Morehouse A R Powell J P Heffer and G Wilkinson J Chem Soc 1965 0 3632ndash3640


17 M T Reetz and E Westermann Angew Chemie Int Ed 2000 39 165ndash168

18 J J Topczewski and M S Sanford Chem Sci 2015 6 70ndash76

19 M Zeng Y Du L Shao C Qi and X-M Zhang J Org Chem 2010 75 2556ndash2563

20 N Miyaura and A Suzuki J Chem Soc Chem Commun 1979 0 866

21 C Amatore A Jutand and M A MrsquoBarki Organometallics 1992 11 3009ndash3013

22 C Amatore A Jutand and A Suarez J Am Chem Soc 1993 115 9531ndash9541

131

23 T Mandai T Matsumoto J Tsuji and S Saito Tetrahedron Lett 1993 34 2513ndash2516

24 D B Eremin and V P Ananikov Coord Chem Rev 2017 346 2ndash19

25 R F Heck J Am Chem Soc 1969 91 6707ndash6714

26 R McCrindle G Ferguson G J Arsenault and A J McAlees J Chem Soc Chem Commun 1983 0 571ndash572

27 T He X Tao X Wu L Cai and V Pike Synthesis (Stuttg) 2008 6 887ndash890

28 T Jeffery Tetrahedron 1996 52 10113ndash10130

29 S Schneider and W Bannwarth Helv Chim Acta 2001 84 735ndash742

30 I Cepanec and I Cepanec Synth Biaryls 2004 139ndash207

31 D A Conlon B Pipik S Ferdinand C R LeBlond J R Sowa B Izzo P Collins G-J Ho J M Williams Y-J Shi and Y Sun Adv Synth Catal 345 931ndash935


33 S N Jadhav A S Kumbhar C V Rode and R S Salunkhe Green Chem 2016 18 1898ndash1911

34 P Zhou H Wang J Yang J Tang D Sun and W Tang RSC Adv 2012 2 1759

35 J Yang and L Wang Dalton Trans 2012 41 12031

36 A Naghipour A Ghorbani-Choghamarani H Babaee and B Notash Appl Organomet Chem 2016 30 998ndash1003

37 P Fitton and E A Rick J Organomet Chem 1971 28 287ndash291

38 C C Ho A Olding J A Smith and A C Bissember Organometallics 2018 37 1745ndash1750

39 N Jana Q Nguyen and T G Driver J Org Chem 2014 79 2781ndash2791

40 Y Uozumi Y Matsuura T Arakawa and Y M A Yamada Angew Chemie Int Ed 2009 48 2708ndash2710

41 R K Arvela and N E Leadbeater Org Lett 2005 7 2101ndash2104

42 N Jamwal M Gupta and S Paul Green Chem 2008 10 999

43 C Schmoumlger T Szuppa A Tied F Schneider A Stolle and B Ondruschka ChemSusChem 2008 1 339ndash347

44 T E Barder S D Walker J R Martinelli and S L Buchwald J Am Chem Soc 2005 127 4685ndash4696

45 K E Balsane S S Shendage and J M Nagarkar J Chem Sci 2015 127 425ndash431

132

5 Heterogenised molecular Pd(II) catalysts for C-H functionalisation


Homogeneous palladium complexes bearing dithiocarbamate ligands have proved to

be effective catalysts for the C-H functionalization reaction of benzo[h]quinoline and

8-methylquinoline under mild and safe conditions over short reaction times (see

Chapter 3)1 However homogeneous catalysis encounters a major drawback in terms

of difficult or expensive recovery processes to separate the catalyst from the product2

As an alternative heterogeneous catalysis generally offers a more reliable cheaper

and straightforward way to separate the catalyst from the reaction mixture for example

through centrifugation or filtration However the often lower activity of heterogeneous

catalysts and the difficulty of surface characterisation and the poorly understood

mechanisms of reaction represent a disadvantage3

The development of a catalytic system with a combination of the properties of both

homogeneous and heterogeneous catalysis systems can be achieved by the

immobilisation of homogeneous catalysts with excellent catalytic activities on the

surface of solid supports4 The immobilisation of active catalysts usually consisting of

metal complexes is often achieved using an organic linker capable of covalently

bonding to the surface of the solid support5 This approach exploits the high catalytic

activity of the homogeneous catalyst while taking advantage of the easy recovery of

an heterogeneous catalyst6-7

In this chapter a new synthetic method for functionalising nanostructures is proposed

in which novel dithiocarbamate salts are obtained by treating two different silyl amine

precursors with carbon disulfide Various spectroscopic techniques will be used to

confirm the formulation of the dithiocarbamate salts As part of our continued interest

in homogenous palladium-based catalysis two simple heteroleptic dithiocarbamate

palladium complexes are reported and investigated structurally using X-ray

crystallography To provide a comparison to our previous work (see Chapter 3) these

palladium(II) complexes are tested in catalyic reactions for the C-H functionalization

of benzo[h]quinoline and 8-methylquinoline By virtue of the silyl moieties attached

these new complexes will be grafted onto the surface of silica (SiO2) and silica-coated

iron-oxide (SiO2Fe3O4) nanoparticles Heterogenisation will be achieved by reaction

133

with the Si-OH binding sites on the silica surface This material will be characterized

using typical physiochemical methods such as infrared (IR) spectroscopy

transmission electron microscopy (TEM) nuclear magnetic resonance (NMR) and

inductively coupled plasma optical emission spectroscopy (ICP-OES)

Successful surface functionalisation will be followed by testing in the C-H activation of

benzo[h]quinoline The difference between homogeneous and heterogeneous

catalytic results will be discussed in detail in this chapter This part of the work was

conducted with the help of an MRes student Kuang Wen Chan

511 Aims and objectives


1 Synthesise heteroleptic palladium complexes bearing dithiocarbamate ligands

and used it as a homogeneous catalyst in C-H functionalization reaction of

benzo[h]quinoline to 10-methoxybenzo[h]quinoline in the presence of the

oxidant PhI(OAc)2

2 Covalently immobilise the heteroleptic palladium complexes onto the surface of

SiO2 and SiO2Fe3O4 nanoparticles This material will be used as a

heterogeneous catalyst in the C-H activation of benzo[h]quinoline


An efficient route to synthesise the novel dithiocarbamate salts

(MeO)3SiCH2CH2CH2(Me)NCS2K (34) and (MeO)3SiCH2CH2CH22NCS2K (35) and

their heteroleptic dithiocarbamate palladium complexes

[(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36) and

[(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37) is described A summary of the

synthetic routes is shown in Figure 521

134

Figure 521 Synthesis of ligands and their palladium dithiocarbamate complexes

521 Synthesis of dithiocarbamate ligands

The commercially available precursors 3-trimethoxysilylpropylmethylamine and

bis(trimethoxysilylpropyl)amine were treated with K2CO3 in acetonitrile for 10 min

before the addition of CS2 The reaction mixtures were stirred for another 2 hours at

room temperature to yield (MeO)3SiCH2CH2CH2(Me)NCS2K (34) and

(MeO)3SiCH2CH2CH22NCS2K (35) respectively as pale yellow solids

Various analytical techniques were employed to confirm the formations of 34 and 35

The most noticeable evidence in the 1H NMR spectrum was the disappearance of the

diagnostic resonances of the secondary amine protons for both precursors at

approximately 33 ppm The retention of the propyl chain in 34 was indicated by a

significant shift of chemical resonances at 064 177 and 402 ppm compared to the

same features in the precursor (at 047 140 and 238 ppm) Furthermore new singlet

resonances at 347 ppm and 355 ppm confirmed the presence of the methyl and

trimethoxy (O-CH3) groups respectively

The 1H NMR spectrum for 35 was dominated by the multiplet resonances of the propyl

chains at 064 183 and 396 ppm (in the precursor 060 154 and 255 ppm)

alongside a singlet resonance at 358 ppm attributed to the trimethoxy (O-CH3)

protons Further characterisation was possible by 13C1H NMR spectroscopy due to

the high solubility of both compounds showing in particular the downfield resonances

at 2109 ppm which were attributed to the CS2 units for both dithiocarbamate salts

135

The solid-state infrared spectrum revealed typical features for dithiocarbamate salts

(ν(C-N) ν(NC=S) and ν(C-S)) for 34 (1461 1267 and 963 cm-1) and 35 (1467 1250 and 965

cm-1) The overall formulation for 34 and 35 was further confirmed by mass

spectrometry which showed molecular ions at mz 268 and mz 416 respectively in

conjunction with good agreement of elemental analysis values

522 Synthesis of Pd(II) complexes bearing dithiocarbamate ligands

The pale-yellow dithiocarbamate salts (34 and 35) were stirred in methanol for 10

minutes To this solution was added a chloroform solution of cis-[PdCl2(PPh3)2]

followed by a methanolic solution of ammonium hexafluorophosphate The reaction

mixtures were heated at reflux for 6 hours and the solvent then removed under

reduced pressure The residues were dissolved in the minimum amount of chloroform

and filtered through Celite and the solvent again removed using a rotary evaporator

Diethyl ether was added to precipitate


[(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37) respectively as pale yellow

products

1H NMR analysis of complex 36 showed the presence of methylene protons resonating

at new chemical shifts (059 171 and 363 ppm) compared to the precursor (064

176 and 402 ppm) In addition the singlet resonances for the methyl and trimethoxy

groups were observed at 321 ppm and 355 ppm respectively alongside the multiplet

aromatic peaks for the coordinated triphenylphosphine at 732 to 747 ppm For

complex 37 a diagnostic singlet resonance attributed to the trimethoxy group was

observed at 352 ppm alongside the multiplet resonances for the methylene protons

(053 168 and 355 ppm) Furthermore the 13C1H NMR spectra revealed that the

resonances for the CS2 units had shifted slightly upfield from 211 ppm to 203 ppm in

both complexes

Analysis by 31P1H NMR spectroscopy confirmed the retention of the

triphenyphosphine ligands For complex 36 the phosphorus nuclei signals were

observed as a pair of doublets at 303 and 306 ppm with a mutual coupling of 350

Hz suggesting a cis-arrangement for the two phosphine ligands In the case of

complex 37 a singlet resonance at 305 ppm was observed due to the chemically

equivalent phosphorus atoms indicating a symmetrical structure

136

Similar IR characteristics were displayed for both complexes particularly the typical

features of dithiocarbamate ligands In addition the vibrational modes associated with

the phenyl rings on the phosphorus centre (962 cm-1) were observed alongside those

of the hexafluorophosphate anion (830 cm-1) was observed Mass spectrometry (ES

+ve ion) displayed a molecular ion at mz 898 and mz 1047 for 36 and 37 respectively

and good agreement of elemental analysis with calculated values further confirmed

the formulation of both complexes

523 Crystal structure of [(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36)

An attempt to grow a suitable crystal of 36 by slow diffusion of diethyl ether into a

concentrated dichloromethane mixture of the complex successfully yielded two

different polymorphic structures assigned as 36-A (Figure 522) and 36-B (Figure

523) The structure of compound [(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25-

A Chapter 3) can be compared directly to those of compounds 36-A and 36-B due to

the similar chelation of the dithiocarbamate ligand towards the palladium centre

Figure 522 The molecular structure of the cation component of [(MeO)3SiCH2CH2CH2(Me)NCS2Pd (PPh3)2]PF6 (36-A) The hexafluorophosphate anions and H-atoms has been omitted to aid clarity

137

Figure 523 The molecular structure of the cation component of [(MeO)3SiCH2CH2CH2(Me)NCS2Pd (PPh3)2]PF6 (36-B) The hexafluorophosphate anions and H-atoms has been omitted to aid clarity

As Table 521 shows comparable Pd-S distances were observed in all complexes

equivalent to the typical bond lengths for dithiocarbamates complexes8 The C-N

bonds of the new complexes range between 1306(4) and 1312(5) Aring slightly lower

than the average bond length for dithiocarbamate compounds (1324 Aring)9 In addition

the average distance of the C-S bonds of 36-A (1722(4) Aring) and 36-B (1721(4) Aring) is

close to that of an average dithiocarbamate complex (1715 Aring)9 Furthermore the S-

Pd-S bite angle of the dithiocarbamate ligand in complex 36 lies in the range 7472-

7492˚ which is close to what is reported for

[(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (7504˚) In contrast a comparable S-

C-S angle for all complexes was recorded

138

Table 521 Tabulated bond lengths and bond angle of compounds 25-A 36-A 36-B

Complexes Pd-S Aring C-N Aring C-S Aring S-C-S˚ S-Pd-S ˚

25-A

23304(10)

23536(10)

1302(5)

1722(4)

1735(4)

1112(2)

7504(4)

36-A

23294(9)

23458(9)

1306(4)

1726(3)

1717(4)

1114(2)

7492(3)

36-B

23293(9)

23476(10)

1312(5)

1719(4)

1722(4)

1111(2)

7472(3)

The two different polymorphic structures both adopt a square planar geometry The

main difference between the structures of 36-A and 36-B is the bond angle of the

trimethoxy group attached to the silicon (Table 522) A noticeable difference is

observed particularly for the C(12)-O(11)-Si(8) and C(14)-O(13)-Si(8) angles which is

illustrated by a difference of 29˚ and 52˚ in bond angle respectively

Table 522 Bond angle (˚) data comparison between complexes 36-A and 36-B

Bond angle 36-A 36-B difference

C(10)-O(9)-Si(8) 1226˚ (5) 1228˚ (7) 02˚

C(12)-O(11)-Si(8) 1220˚ (5) 1249˚ (6) 29˚

C(14)-O(13)-Si(8) 1221˚ (6) 1273˚ (7) 52˚

524 Crystal structure of [(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37)

Vapour diffusion of hexane into a concentrated dichloromethane solution of the

complex successfully generated a single crystal of

[(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37) suitable for X-ray analysis (Figure

524) A direct comparison with 36-B was made and this revealed a similar square

planar geometry The Pd-S (23312(8) and 23603(8) Aring) C-N (1310(5) Aring) and C-S

139

(1724(4) and 1724(3) Aring) bond lengths are found to be comparable between both

complexes However the S-C-S angle (11213˚) and S-Pd-S bite angle (7514˚) value

of 37 are slightly greater compared to the structure of 36-B

Figure 524 The molecular structure of the cation component of [(MeO)3SiCH2CH2CH22NCS2Pd (PPh3)2]PF6 (37) The hexaflorophosphate anions and H-atoms has been omitted to aid clarity

53 Catalytic activity of heteroleptic palladium complexes

Work within the group1 has demonstrated the ability of Pd(II) complexes bearing

dithiocarbamate ligands to act as effective catalysts for the C-H functionalization of

benzo[h]quinoline and 8-methylquinoline (see Chapter 3) This prompted us to explore

the catalytic activity of the palladium complexes presented in this chapter (36 and 37)

as homogeneous catalysts for C-H activation of the same compounds (Figure 531)

140


To study the reaction parameters we used benzo[h]quinoline as a substrate (Figure

531 Reaction A) Yields of 85 were obtained after 2 hours using 1 mol of 36 or

37 PhI(OAc)2 as an oxidant and methanol as a solvent at 100 degC A comparable

catalytic activity (87 product yield) was reported by us1 using

[Pd(S2CNEt2)(PPh3)2]PF6 (23) under the same reaction conditions in Chapter 3 (Table

531) This finding proved that the complexes have an excellent catalytic activity

towards C-H oxidative functionalisation reactions However working at high

temperature is undesirable due to the energy consumption and safety issues

(excessive pressures) Thus the catalytic reaction was optimised to operate at lower

reaction temperatures varying the loading of catalyst in Section 531

Table 531 Results for the methoxylation of benzo[h]quinoline Catalysts = 23 36 and 37

Reaction

Catalyst Pd

(mol)

Temperature

(degC)

Time

(h)

Yield

()

SD

A

36

1

100

2

85 ( 06)

37 85 ( 07)

23 87 (10)

141

531 Optimisation of reaction conditions

The effect on the reaction time was investigated by dissolving 1 mol of the catalysts

(36 and 37) benzo[h]quinoline and PhI(OAc)2 in methanol The reaction mixture was

heated and stirred for 2 to 5 hours Figure 532 shows an increasing trend in product

yield as a consequence of increasing the reaction time However a low yield of product

(gt 55) was obtained even after 5 hours of reaction at a lower temperature for both

palladium catalysts This finding suggests that lowering the temperature of the reaction

reduces the rate of dissociation of the triphenylphosphine ligand to form an active

catalytic intermediate resulting in a lower yield of product Based on our previous

report1 an increase in catalyst loading is required to achieve a quantitative yield of

product

Figure 532 The effect of reaction time on the yield of the desired product Catalysts = 36 and 37 (1 mol) solvent = MeOH oxidant = PhI(OAc)2 T = 50 degC

The influence of catalyst loading on the reaction was examined using 1 to 5 mol of

the catalysts (36 and 37) in the same C-H functionalization reaction with

benzo[h]quinoline as the substrate The reaction mixtures were heated and stirred for

2 hours in the presence of PhI(OAc)2 In general the yield of the product increased

with the increase in catalyst loading from 1 to 5 mol Figure 533 reveals that 3 mol

of 36 or 37 was effective providing a high yield (gt 85) of the desired product within

0

10

20

30

40

50

60

70

1 2 3 4 5 6

Yiel

d (

)

Time (hours)

36 37

142

2 hours at 50 degC Lower catalyst loadings (1 mol) lead to a lower conversion of the

product (lt 30) Overall both catalysts demonstrated excellent catalytic activity under

milder (50 degC) and safer (low pressure) conditions and required a shorter reaction time

(2 h) for the methoxylation of benzo[h]quinoline compared to the more forcing reaction

conditions used in the literature (100 degC 12 mol 22 h)10 Based on this catalytic

performance the standard operating conditions (SOCDTC) for both catalysts was set

at 3 mol Pd loading at 50 degC for 2 hours

Figure 533 The effect of catalyst loading on the yield of the desired product Catalyst = 36 and 37 solvent = MeOH oxidant = PhI(OAc)2 T = 50 degC t = 2h

532 Other alkoxy functionalisation of benzo[h]quinoline

Having established the SOCDTC the scope of the reactions was expanded to other

alkoxy functionalisations of benzo[h]quinoline However the overall findings

suggested that the introduction of more sterically demanding moieties (R = OEt O iPr

and CH2CF3) required a longer reaction time to produce the desired products

compared to the optimum conditions (Table 532) For example a quantitative yield

of 10-ethoxybenzo[h]quinoline (99) could only been achieved after 24 hours

compared to the 89 yield obtained using [Pd(S2CNEt2)(PPh3)2]PF6 (23) under the

same reaction conditions (3 mol catalyst loading 50 degC 2 h) In addition more than

90 conversion to 10-trifluoroethoxybenzo[h]quinoline was obtained after 6 h for both

0

20

40

60

80

100

120

0 1 2 3 4 5 6

Yiel

d (

)

Catalyst loading (mol)

36 37

143

catalysts In summary the catalytic performances of complexes 36 and 37 are slightly

lower compared to that displayed by the complex [Pd(S2CNEt2)(PPh3)2]PF6 (23)

reported1 in Chapter 3

The analysis of the methoxylation of 8-methylquinoline produced a slightly lower

conversion (60) of product by employing 37 as a catalyst after 6 hours reaction which

can be achieved by 23 in a far shorter reaction time (2 h)

Table 532 Catalytic results for Reaction A employing 23 36 and 37 (3 mol) as catalysts Oxidant = PhI(OAc)2 T = 50 degC


(h)

Yield

()

SD

Et

23 2 89 (20)

A

36 24 99 (04)

37 24 42 (34)

CH2CF3

23 4 92 (10)

36 6 98 (02)

37 6 90 (17)

B Me 23 2 66 (02)

37 6 60 (38)

54 Supported catalyst design

Both monometallic homogeneous palladium catalysts (36 and 37) showed excellent

catalytic behaviour for the methoxylation of benzo[h]quinoline However

homogeneous catalysis often faces difficult recovery from reaction mixture leading to

possible contamination of the products and requiring further (often costly or time

consuming) purifcation processes In an industrial context constant exposure to high

temperature and pressure in the reaction vessel might also lead to catalyst

decomposition limiting their applications11

The heterogenisation of homogeneous catalysts on the surface of supporting materials

can be viewed as a solution to this problem harnessing the best of both homogeneous

and heterogeneous systems SiO2Fe3O4 nanoparticles were chosen as potential

supports to immobolise the active palladium catalysts (36 and 37) allowing a similar

catalytic activity to be combined with the ease of recovery of the catalyst Silica

nanoparticles are straightforward to prepare using the well-known Stoumlber method12

144

and the separation of used nanoparticles can be achieved with a simple filtration In

addition SiO2Fe3O4 nanoparticles can be prepared through a slight modification of

the co-precipitation procedure reported in the literature13 The magnetic nanoparticles

can be easily separated from the reaction mixture through the presence of an external

magnetic field14

The immobilisation of metal units on silica and SiO2Fe3O4 has been described

through two simultaneous reactions (i) the hydrolysis of the alkoxy groups on the

Si(OCH3)3 unit to the corresponding reactive silanol species [Si(OH)3] and (ii) the

condensation of the resultant silanol species with the free hydroxyl groups on the silica

surface to form stable Si-O-Si bonds15 Figure 541 represents the presence of 36 and

37 tethered to the surface of silica-coated iron oxide nanoparticles These immobilised

catalysts were then tested in the C-H functionalization of benzo[h]quinoline

Figure 541 Diagram showing the attachment of 36 and 37 on the surface of silica coated iron-oxide nanoparticles

541 Synthesis of SiO2 nanoparticles

Following the Stoumlber sol-gel process12 tetraethylorthosilicate (TEOS) was added to a

low molar-mass alcohol (ethanol) in the presence of water before the addition of

aqueous ammonia solution The reaction mixture was stirred at room temperature for

3 h to yield a white precipitate16 The product was separated by centrifugation washed

with ethanol and dried under reduced pressure to give colourless silica nanoparticles

145

The morphology of the silica nanoparticles was determined by transmission electron

microscopy (TEM) As illustrated in Figure 543 the formation of spherical silica

nanoparticles with an average size of 201 plusmn 40 nm This value is within the typical

average size range of silica nanoparticles (50 to 2000 nm) reported using the Stoumlber

method171819 Further analysis of the sample using infrared spectroscopy revealed

typical absorption bands arising from the asymmetric vibration of Si-O (1056 cm-1) the

asymmetric vibration of Si-OH (952 cm-1) and the symmetric vibration of Si-O (799

cm-1) The absence of absorption bands for CH3 (2980 cm-1) and CH2 (2930 cm-1) of

unreacted TEOS confirmed the efficacy of the washing procedure while intense

absorption bands for water (3300-3500 cm-1) were also observed19

Figure 543 TEM images of silica nanoparticles synthesised using the Stober method

542 Synthesis of magnetic nanoparticles

According to a literature procedure20 the Fe3O4 nanoparticles were prepared by the

co-precipitation method of Fe2+Fe3+ ions A solution of FeCl3 in fresh deoxygenated

water was treated with an acidic solution of FeCl2 This was followed by the addition

of an ammonium hydroxide solution (precipitating agent) to the reaction mixture under

vigorous stirring for 30 min at room temperature The whole process was conducted

under a nitrogen environment to avoid any further oxidation of the Fe3O421 The

resulting black precipitate was separated magnetically and oleic acid (capping agent)

was introduced to stabilise and control the size of the nanoparticles22 The reaction

mixture was heated for another 30 min at 80 degC and the resulting black precipitate was

146

washed with acetone and re-dissolved in toluene The solution was centrifuged and

the supernatant liquid was evaporated to dryness to give brown Fe3O4 magnetic

nanoparticles

The morphology and the distribution of Fe3O4 nanoparticles were characterised by

TEM and are shown in Figure 544 The images show the formation of uneven shaped

nanoparticles with an average diameter of approximately 80 plusmn 30 nm To investigate

the coating of oleic acid on the surface of Fe3O4 FT-IR measurements were

conducted The spectra revealed two sharp diagnostic absorption bands at 2919 and

2850 cm-1 which were attributed to the asymmetric and symmetric CH2 stretch

respectively The presence of absorption peaks at 1568 and 1695 and cm-1 was

ascribed to asymmetric and symmetric carboxylate stretches confirming the bonding

of the carboxylic acid to the magnetic nanoparticles An absorption at 1089 cm-1 was

assigned to the C-O single bond stretching mode A diagnostic peak associated with

the Fe-O stretching band in the region 560-600 cm-1 further confirmed the formation

of nanoparticles2324 These Fe3O4 nanoparticles were then used in the preparation of

silica-coated Fe3O4 nanoparticles

Figure 544 TEM images showing the Fe3O4 synthesised by the co-precipitation method

147

543 Synthesis of SiO2Fe3O4 nanoparticles

The SiO2Fe3O4 nanoparticles were prepared using a slight modification of the

microemulsion technique described in the literature2526 The discontinuation of

production of the non-ionic surfactant IGEPAL 520-A led to the use of Triton X-45

(possessing an identical chemical formula) in the synthesis of SiO2Fe3O4

nanoparticles The non-ionic surfactants were dispersed in cyclohexane which serves

as a phase transfer agent for oleic acid-capped Fe3O427 The readily-prepared Fe3O4

nanoparticles were dissolved in cyclohexane and transferred to the reaction

suspension Triton X-45 encompasses a polyoxyethylene moiety with a terminal

hydroxyl group as the hydrophobic section and a long hydrocarbon chain as the

hydrophilic tail This structure enabled the agglomeration process to proceed in an

ordered fashion through the weak hydrogen bonding of the hydroxyl groups with the

surface of Fe3O4 while the hydrophobic tails remained parallel interacting with each

other to stabilise the entire system28 On addition of ammonia a microemulsion

process occurred TEOS was added and the reaction mixture stirred for another 16

hours allowing the hydrolysis and condensation of TEOS to induce silica growth on

the surface of Fe3O4 The addition of methanol caused the precipitation of

Fe3O4SiO2 nanoparticles which were separated by centrifugation and washed with

ethanol and dried

Figure 545 shows the TEM micrographs of the Fe3O4 nanoparticles encapsulated

within the silica sphere The average diameter of the SiO2Fe3O4 core-shell

nanoparticles was determined to be 410 plusmn 43 nm FT-IR studies revealed the

characteristic absorption peaks at 560-600 cm-1 associated with the Fe-O stretching

mode as well as bands related to the silica nanoparticles The strong bands at 1055

cm-1 and 796 cm-1 were attributed to asymmetric and symmetric vibrations of Si-O

while the asymmetric Si-OH vibration was detected at 952 cm-1 further confirming the

formulation of SiO2Fe3O4 nanoparticles

148

Figure 545 TEM image showing the SiO2Fe3O4 core-shell nanoparticles


Complexes 36 and 37 were added to silica nanoparticles in toluene under nitrogen

and the reaction mixtures were stirred at reflux overnight The solutions were allowed

to cool to room temperature and the resulting yellow precipitate (unattached surface

units) were separated by centrifugation The products were washed with chloroform

and dried

For both compounds (36 and 37) the intense absorption band of triphenylphosphine

was observed at 690 cm-1 in the IR spectra However the FT-IR spectrum after the

surface modification showed only a small absorption for the most intense bands of

PPh3 which indicated that only a small number of palladium complexes were present

on the silica surface Bands usually associated with the phenyl rings attached to the

phosphorus centre (962 cm-1) were not observed due to the broad signal assigned to

asymmetric vibration of Si-O centred around 1050 cm-1 Finally two shoulder bands

at 950 cm-1 and 800 cm-1 were observed and these are compatible with the asymmetric

vibration of Si-OH and the symmetric vibration of Si-O in the original silica

nanoparticles FT-IR spectrum The changes in the IR spectrum (after functionalisation)

indicated that both palladium complexes were successfully attached on the silica

nanoparticles surface

Another important observation is the difference in colour of the silica nanoparticles

before and after surface modification with complex 36 Figure 547 shows the pure

149

silica nanoparticles as a colourless solution compared to a yellow colouration for the

solution of SiO236 (both in chloroform) This observation further confirmed that the

palladium complexes were coordinated to the surface of the SiO2 nanoparticles

providing support for the analogous functionalisation of complexes 36 and 37 on the

surface of paramagentic Fe3O4silica coated nanoparticles

Figure 547 Colour comparison between a solution of SiO2 nanoparticles (left) and SiO236 nanoparticles (right)

545 Surface functionalisation of SiO2Fe3O4 nanoparticles with palladium

complexes

Encouraged by the successful modification of the silica nanoparticle surface

SiO2Fe3O4 nanoparticles were functionalised with palladium complexes (36 and 37)

using the same procedure The resulting precipitates were collected by centrifugation

and washed with chloroform to remove any unattached molecular palladium complex

As shown in Figure 548 37SiO2Fe3O4 only required six washings with 5 mL of

chloroform to give a colourless solution However 36SiO2Fe3O4 required

approximately eight chloroform washings before the solution became colourless This

finding could suggest a weaker binding of 36 on the nanoparticle surface compared to

37 possibly due to the presence of two trimethoxysilyl moieties interacting with the

hydroxyl groups on the surface of SiO2Fe3O4 The colourless washings suggest the

removal of all uncoordinated complexes and indicate that the remaining surface units

are covalently bonded (chemisorbed) to the surface of nanoparticles rather than

physisorbed

150

Figure 548 Washing solutions of 36SiO2Fe3O4 (top) and 37SiO2Fe3O4 (bottom)

The modified SiO2Fe3O4 nanoparticles were characterised using FT-IR

spectroscopy A small vibration for triphenylphosphine at 690 cm-1 was the only signal

observed clearly ascribable to the complexes However significant changes in the

asymmetric vibration of Si-O (changed from 1055 to 1063 cm-1) and asymmetric

vibration of Si-OH (changed from 952 to 944 cm-1) suggest a modulation in the

environment of the materials NMR analysis of the samples was not carried out due to

the paramagnetic properties of the SiO2Fe3O4 nanoparticles29 Electron microscopy

(Figure 549) was not able to indicate the presence of the surface units (36 or 37) but

showed the Fe3O4 core remaining encapsulated in the spherical shape of the silica

nanoparticles

Figure 549 TEM image of immobilised palladium complexes 36 (left) and 37 (right) on the surfaces of SiO2Fe3O4 nanoparticles

151

The SiO2Fe3O4 nanoparticles bearing palladium complexes (36 and 37) were further

characterized by TGA analysis The results for 36SiO2Fe3O4 show a slow decline

in mass from 100 to 210 degC followed by a considerable loss between 210 to 300 degC

which can be attributed to surface unit decomposition The loss in mass is relatively

stable until the end of the analysis (300 to 600 degC) The approximately 17 loss in

mass over the whole process can be attributed to the loss of the surface unit (excluding

palladium and silica) TGA data for 37SiO2Fe3O4 revealed a metallic residue of

67 of the original mass with the remaining 33 of the mass coming from the rest of

elements in the surface units (excluding silica and palladium) The fact that the mass

loss is around double for 37 than for 36 suggests greater stability for the former (with

two attachment points) compared to the latter

Figure 5410 TGA analysis of SiO2Fe3O4 nanoparticles bearing palladium units

The key features of these systems include convenient magnetic recovery of the

immobilised palladium catalyst units avoiding the use of additional separation

techniques (filtering centrifugation etc) as well as helping prevent the loss of catalyst

units Thus the ability of the SiO2Fe3O4 nanoparticles functionalised by palladium

surface units to be recovered by a hand-held magnet was tested This was achieved

by dissolving a small amount of 37SiO2Fe3O4 in chloroform and shaking until a

brownish-yellow mixture was obtained (Figure 5411) Notably the magnetic

nanoparticles responds to an external magnetic field as anticipated boding well for

the their magnetic separation from solution

60

65

70

75

80

85

90

95

100

0 100 200 300 400 500 600

Weig

ht (

)

Temperature ()

36Fe₃O₄SiO₂ 37Fe₃O₄SiO₂

152

Figure 5411 Recovery of immobilised palladium complex on 37SiO2Fe3O4 nanoparticles

546 Methoxylation of benzo[h]quinoline employing an immobilised

palladium catalyst

The palladium content in 36SiO2Fe3O4 and 37SiO2Fe3O4 was determined

using ICP-OES Approximately 1 mg of sample was dissolved in a solution of aqua

regia (3 mL HCl 1mL of HNO3) and the mixture was then stirred and heated at 100

degC for 2 hours and then diluted with de-ionised water to decrease the concentration of

acid to less than 10 (vv)30 According to the analysis the palladium unit contributed

90 and 100 of the total mass of 36SiO2Fe3O4 and 37SiO2Fe3O4

respectively (Appendix B and C) These data were used to calculate the amount of

compound necessary for the catalyst loading for the methoxylation of

benzo[h]quinoline employing the SOC DTC reported in Section 531 (3 mol 50 degC 2

h)

The conversion of the reactant to product calculated by 1H NMR analysis are shown

in Table 541 Substantially lower conversions (32 in both cases) were obtained

using 36SiO2Fe3O4 and 37SiO2Fe3O4 as the catalyst systems If compared

to the yields of the homogenous catalysts 36 (87) and 37 (88) alone these data

indicate a large decrease in yield under the same reaction conditions A contributing

factor was thought to be the insolubility of the heterogenised catalyst system which

might affect the accessibility of the substrate molecule to the active sites

153

Table 541 Methoxylation of benzo[h]quinoline using 36SiO2Fe3O4 and 36SiO2Fe3O4 employing SOCDTC

SystemRun numbers 1 2 3 4

36SiO2Fe3O4 32 13 5 -

36SiO2Fe3O4 32 27 10 6

A recycling experiment was performed to investigate the catalyst performances in

subsequent runs under identical conditions It was achieved by the separation of

immobilised catalyst from the reaction mixture by external magnet It was followed by

the introduction of benzo[h]quinoline PhI(OAc) and methanol into the same vials

containing the immobilised palladium catalyst Unexpectedly it was found that the

yields decreased over subsequent runs 36SiO2Fe3O4 recorded almost a one-

third decrease in product yield after a second cycle and gave no conversion in the

fourth cycle suggesting a quicker deactivation of the immobilised catalyst compared

to 37SiO2Fe3O4 which still gave a low yield (6) after the fourth cycle Further

investigation was carried out by analysing the reaction mixture after the 4th run

containing 37SiO2Fe3O4 with 31P1H NMR spectroscopy showing the presence

of a singlet peak belonging to the molecular catalyst at 30 ppm proof of palladium

leaching Additionally the ICP-OES analysis of isolated spent catalyst

(37SiO2Fe3O4) revealed a decrease of palladium loading to 28 of total mass

which further supports the idea of a loss of surface units from the SiO2Fe3O4

support This could be due to mechanical damage to the silica shell causing loss of

catalyst units which are removed after each run Another possible explanation for

these findings is that the surface units are bonded to the SiO2Fe3O4 nanoparticle by

strong physisorption rather than covalently bonded (chemisorption) as initially

hypothesised and are also lost

Since it was hypothesised that the surface unit might not be covalently bonded onto

the surface palladium complex 37 was functionalised on the surface of SiO2Fe3O4

using chloroform instead of toluene as a solvent in which 37 is more soluble The

calculated ICP-OES result revealed an approximately 72 mass contribution from

the palladium complexes attached to the nanoparticle surface This material was then

used as a catalyst in the methoxylation of benzo[h]quinoline using SOCDTC (3 mol

154

50 degC 2 h) The conversion to 10-methoxybenzo[h]quinoline was recorded at 18 for

the first run and 15 for a subsequent run with recycled catalyst This catalytic result

was lower than the previous experiment which suggesting a similar leaching

behaviour In a separate experiment freshly prepared 36SiO2Fe3O4 was used as

a catalyst for the methoxylation of benzo[h]quinoline under optimum conditions but for

an extended reaction time (22 h) The yield of 76 is the highest achieved using an

immobilised catalyst in this study but is still lower compared to the corresponding

homogeneous catalyst (36)

55 Conclusion

The novel approach described here utilises the properties of silyl amine-based

dithiocarbamates (34 and 35) to construct heteroleptic palladium complexes (36 and

37) in a controlled stepwise manner Single crystals of palladium complexes 36 and

37 were obtained and their structures determined These palladium(II) complexes

were shown to be effective catalysts in the methoxylation of benzo[h]quinoline under

milder (50 degC) and safer (low pressure) conditions over shorter reaction times (2 h)

yielding more than 85 of product compared to the same yield in the literature which

requires much more forcing conditions (100 degC 12 mol 22 h) However other

alkoxy functionalization reactions of benzo[h]quinoline using more sterically

demanding moieties (EtOH i-PrOH and CF3CH2OH) required a longer reaction time

than that needed for the methoxylation of benzo[h]quinoline

The potential of the NR2 substituents of the coordinated dithiocarbamate ligand were

explored by extending the scope of the studies to heterogeneous catalysis This was

achieved by the immobilisation of the heteroleptic palladium complexes 36 and 37 on

core-shell SiO2Fe3O4 nanoparticles These novel constructs 36SiO2Fe3O4 and

37SiO2Fe3O4 were successfully synthesised and characterised using FT-IR

TEM ICP-OES and TGA The mass contribution of the palladium surface units on

36SiO2Fe3O4 and 37SiO2Fe3O4 nanoparticles was found to be 90 and

100 respectively However a lower catalytic activity was found for both

nanoparticle systems compared to the homogeneous catalysts (36 and 37) in identical

methoxylation reactions using benzo[h]quinoline as the substrate It was hypothesised

155

that loss of palladium surface units had occurred leading to the deactivation of the

catalyst Further investigation is required to understand exactly how this occurred and

whether it was due to mechanical damage or weakly attached surface units Once

addressed this approach could be used more widely to generate heterogenised

molecular catalyst species using silyl-functionalised dithiocarbamate units as tethers

156

56 References



3 G Ertl H Knoumlzinger and J Weitkamp Handbook of Heterogeneous Catalysis Vol 3 1997

4 R A Shiels and C W Jones in Model Systems in Catalysis Springer New York New York NY 2010 pp 441ndash455

5 S Shylesh V Schuumlnemann and W R Thiel Angew Chemie Int Ed 2010 49 3428ndash3459








13 M J Jacinto P K Kiyohara S H Masunaga R F Jardim and L M Rossi Appl Catal A Gen 2008 338 52ndash57

14 A Lu E Salabas and F Schuumlth AngewChemIntEd 2007 46 1222ndash1244

15 I A Rahman and V Padavettan J Nanomater 2012 2012 1ndash15


17 S K Park K Do Kim and H T Kim Colloids Surfaces A Physicochem Eng Asp 2002 197 7ndash17

18 I A Rahman P Vejayakumaran C S Sipaut J Ismail M A Bakar R Adnan and C K Chee Colloids Surfaces A Physicochem Eng Asp 2007 294 102ndash110

19 J W Kim A L U Kim and C K Kim Biomacromolecules 2006 7 215ndash222

20 A P Philipse M P B van Bruggen and C Pathmamanoharan Langmuir 1994 10 92ndash99

21 L M Rossi L L R Vono F P Silva P K Kiyohara E L Duarte and J R Matos Appl Catal A Gen 2007 330 139ndash144

22 M Bloemen W Brullot T T Luong N Geukens A Gils and T Verbiest J

157

Nanopart Res 2012 14 1100

23 A K Bordbar A A Rastegari R Amiri E Ranjbakhsh M Abbasi and A R Khosropour Biotechnol Res Int 2014 2014 705068

24 L Zhang R He and H-C Gu Appl Surf Sci 2006 253 2611ndash2617


26 M J Jacinto R Landers and L M Rossi Catal Commun 2009 10 1971ndash1974

27 F Ye S Laurent A Fornara L Astolfi J Qin A Roch A Martini M S Toprak R N Muller and M Muhammed Contrast Media Mol Imaging 2012 7 460ndash468

28 S Santra R Tapec N Theodoropoulou J Dobson A Hebard and W Tan Langmuir 2001 17 2900ndash2906

29 M Du and Y Zheng Polym Compos 2007 28 198ndash207

30 S Goddard and R Brown Sensors 2014 14 21676ndash21692

158


61 Conclusions

This chapter gathers together the conclusions of the research carried out in the thesis

The aim and objectives of the research outlined in each chapter are reviewed and

their achievements addressed

In Chapter 2 the reactivity of different donor groups (oxygen nitrogen and sulfur) in

generating multimetallic assemblies was explored The dithiocarbamate ligand

[KS2CN(CH2py)2] was employed as a scaffold to generate seven different novel

monometallic complexes with different geometries all fully characterised However

the insertion of a second metal into the assemblies through the bidentate nitrogen

donor was unsuccessful This led us to a change in strategy and exploration of the

reactivity of the polyfunctional dicarboxylate ligand H2dcbpy The successful formation

of seven new multimetallic complexes three of them heteromultimetallic was

achieved thanks to the strong affinity of carboxylate and nitrogen moieties to

coordinate the Ru and Re centres respectively Successively five new complexes

three bi- and two trimetallic employing Ru Re andor Au as metal centres were

synthesised employing the sulfur and carboxylate donors of 4-mercaptobenzoic acid

Finally a ruthenium complex containing a disulfide linker was successfully attached to

the surface of gold and palladium nanoparticles in a facile manner Overall this

constituted a stepwise generation of multimetallic assemblies using variety of different

donor groups

Chapter 3 described the development of a greener approach to C-H functionalization

using using palladium(II) dithiooxamide complexes as catalysts These were obtained

directly from the metal recovery process used to recycle the palladium content of used

three-way automotive catalytic converters In addition two mono- and two bimetallic

Pd(II) dithiocarbamate complexes were synthesised and showed excellent catalytic

activity in the methoxylation of benzo[h]quinoline Notably the milder and safer

reaction approach (50 degC 2-3 mol 2 h) adopted in this research produced a similar

or higher yield of the product compared to the more forcing and energy-intensive

conditions (100 degC 1-5 mol 18-27 h) used in the literature

159

The use of the commercially available reagent tetrabutylammonium iodide (TBAI) and

iodine to recover palladium waste from spent catalytic converters was demonstrated

in Chapter 4 The bimetallic complex (TBA)2[Pd2I6] obtained from the recovery

process demonstrated excellent catalytic activity in the C-H functionalization and

Suzuki-Miyaura cross-coupling reactions A novel route to synthesise a variety of

Pd(II) analogues via simple ligand exchange reactions between (TBA)2[Pd2I6] and

phosphine ligands was developed These complexes showed a good catalytic activity

towards Suzuki-Miyaura cross-coupling reactions with different substrates

The preparation of novel palladium catalysts bearing dithiocarbamate ligands is

described in Chapter 5 These complexes were then used to functionalise the surface

of core-shell iron-oxidesilica nanoparticles The unsupported systems provided a

quantitative yield of product for the methoxylation of benzo[h]quinoline under mild

conditions (50 degC 3 mol 2 h) However the supported catalyst systems recorded a

lower yield of product using the same reaction conditions A possible explanation to

these findings is the loss of palladium surface units possibly through mechanical

damage while stirring which leads to deactivation of the heterogeneous catalyst

system

62 Future work

The greener approach to performing organic functional group transformations

described here is based on the direct use of the palladium complexes obtained from

the recovery process This innovation should reduce the environmental and financial

cost of catalyst production as well as reducing the reliance on energy-intensive and

environmentally-damaging mining Thus future work can focus on optimising this

process to provide active catalysts for a variety of other reactions such as

Sonogashira Heck and Stille couplingsSimilar approaches could also be used to

valorise gold from waste electrical and electronic equipment (WEEE)

The approach to immobilising palladium complexes on the surface of nanostructures

using the silyl tethers reported in Chapter 5 is promising but needs to be optimised

Further investigation is required to understand the loss of palladium observed Future

work will focus on the exploration of different types of support that can be used for

160

immobilising the Pd surface unit as well as a more robust or reactive linker to ensure

secure attachment of the palladium surface unit to the support

161

7 Experimental

71 General considerations

The nuclear magnetic resonance (NMR) and single X-Ray crystallographic analysis

were run by Mr Pete Haycock and Dr Andrew White respectively at Imperial College

London Mr Stephen Boyer performed all the elemental analysis at London

Metropolitan University Mass Spectrometry and Inductive Coupled Plasma were

analysed by the generous help of Dr Lisa Haigh and Dr Patricia Carry at Imperial

College London Transmission Electron Microscopy and Energy Dispersive X-ray

spectroscopy were analysed with the help of Dr Caterina Ware and Dr Andrew Rogers

at Imperial College London and Old Brompton Hospital respectively

For simplicity full characterisation of the compounds is divided into different sections

consistent with the chapter in this thesis

72 Materials and methods

All the chemicals and solvents were purchased from Alfa-Aesar Sigma-Aldrich

Flurochem or VWR and were used without further purification unless otherwise stated

All experiments and manipulations of compounds were conducted in the air unless

otherwise specified All moisture and oxygen sensitive compounds were prepared

using standard Schlenk line and cannula techniques The products obtained appear

indefinitely stable towards the atmosphere whether in solution or the solid state

Johnson Matthey Ltd and Tom Welton Group are gratefully acknowledged for the

generous loan of ruthenium trichloride and bis(triphenylphosphine)palladium(II)

dichloride respectively

Compounds cis-[RuCl2(dppm)2]1 [RuHCl(CO)(BTD) (PPh3)2]2

[Ru(CH=CHC6H4Me4)Cl(BTD)(CO)(PPh3)2]3 [Ru(C(CequivCPh)=CHPh)Cl(CO)(PPh3)2]4

[Ru(CH=CHPyr-1)Cl(CO)(BTD)(PPh3)2]5 [RuCH=CH-

bpyReCl(CO)3Cl(CO)(BTD)(PPh3)2]6 [Re(dcbpy)(CO)3Cl]6 [ReCl(CO)3(bpy CequivCH]7

[Pd(S2CNEt2)(PPh3)2]PF68 [Pd(S2CNEt2)2]9 [Pd(Me2dazdt)2]I610 [PdI2(Me2dazdt)]10

[AuCl(PPh3)]11 [PtCl2(PPh3)2]12 [Au(SC6H4CO2H-4)2]PPN1314 [Au(SC6H4CO2H-

4)(PPh3)]1516 and [AuCl(tht)]17 (SC6H4CO2H-4)218 KS2CNC4H8NCS2K19

162

KS2CN(Bz)CH2CH2N(Bz)CS2K20 NNrsquo- dimethyl perhydrodiazepine-23-dithione

diiodide adduct (Me2dazdt)21 and di-(2-picolyl)amine22 were prepared according to

literature procedures All glassware used for nanoparticle preparation was washed

with aqua regia and rinsed thoroughly with ultrapure water before use Petroleum ether

refers to the fraction boiling in the range 40minus60 degC

Infra-red spectra were recorded on Perkin Elmer Spectrum 100-FT-IR Spectrometer

with 16 scans at range 600 to 4000 cm-1 on solid samples Nuclear magnetic

resonance (NMR) analysis were performed at 25 degC using Varian Bruker AV400 and

Bruker 500 Avance III HD spectrometers in deuterated CDCl3 unless stated otherwise

Chemical shifts and coupling constants in NMR spectra are reported in part per million

(ppm) and Hertz (Hz) respectively The chemical resonances attributed to

tetraphenylborate (BPh4ˉ) and hexafluorophosphate (PF6ˉ) in 31P1H NMR spectrum

were observed in the formulation but are not reported Elemental analysis

measurements were conducted at London Metropolitan University A Micromass

Autospec and Waters LCT Premier ES-ToF was employed to gather mass

spectrometry data (ES and MALDI-TOF) Transmission Electron Microscopy (TEM)

images and Energy Dispersive X-ray spectroscopy (EDX) data for nanoparticles were

obtained using a JEOL 2010 high-resolution TEM (80minus200 kV) equipped with an

Oxford Instruments INCA EDS 80 mm X-Max detector system Thermogravimetric

analysis (TGA) and Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-

OES) analyses were performed on a Mettler Toledo DSC 1LFUMX

Thermogravimetric Analyzer and a PerkinElmer 2000 DV ICP-OE spectrometer

respectively X-ray Crystallography analyses were performed on a Rigaku Micromax

007HF-M high-flux generator equipped with Rigaku Saturn 944+ CCD and MAR345

image plate detector

163

73 Synthesis of compounds in Chapter 2

731 KS2CN(CH2py)2 (1)

A mixture of di-(2-picolyl) amine (100 mg 05 mmol) and K2CO3 (276 mg 20 mmol)

in acetonitrile (40 mL) was treated with carbon disulfide (0037 mL 06 mmol) The

resultant yellow mixture was stirred for 1 h at room temperature after which it was

filtered to give a clear yellow solution The solvent was removed under reduced

pressure until a thick yellow liquid was obtained The crude oil was dissolved in the

minimum amount of chloroform and filtered through Celite to remove unreacted K2CO3

The solvent was removed to yield the product as a yellow-greenish liquid Yield 132

mg (84) IR 2923 (νC-H) 2361 1591 1570 1474 1434 (νC-N) 1358 1302 1183

1094 1049 998 (νC-S) 987 (νC-S) 847 751 cmndash1 1H NMR (CDCl3) 559 (s 4H

NCH2) 704 (m 2H py-H5) 730 (d 2H py-H3 JHH = 78 Hz) 753 (td 2H py-H6 JHH

= 78 18 Hz) 845 (m 2H py-H4) ppm 13C1H NMR (CDCl3) 2160 (s CS2) 1572

1493 1368 1224 1221 547 (s NCH2) ppm MS (ES -ve) mz (abundance) 2741

(100) [M-K]ˉ

732 [Au(S2CN(CH2py)2)(PPh3)] (2)

A methanolic solution of KS2CN(CH2py)2 (601 mg 0192 mmol) was treated with

[AuCl(PPh3)] (797 mg 0161 mmol) in dichloromethane (10 mL) and stirred at room

temperature for 2 h in the dark All solvent was removed and the resultant residue

was dissolved in dichloromethane (3 mL) and filtered through Celite to give a green

solution All solvent was evaporated to give the product as a green solid which was

dried under vacuum Yield 62 mg (53) IR 2923 (νC-H) 1901 1590 1475 (νC-N)

1434 1202 1098 994 (νC-S) 744 691 cmndash1 1H NMR (CDCl3) 537 (s 4H NCH2)

723 (m 2H py-H5) 732-764 (m 30H+2H C6H5 + py-H3) 774 (td 2H py-H6 JHH =

76 17 Hz) 858 (d 2H py-H4 JHH = 48 17 Hz) ppm 31P1H NMR (CDCl3) 356

(s PPh3) ppm MS (ES +ve) mz (abundance) 734 (100) [M+1]+ Elem Anal Calcd

for C31H27AuN3PS2 (Mw = 73364) C 508 H 37 N 57 Found C 506 H 36

N 56

164

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3)

A solution of [PtCl2(PPh3)]2 (50 mg 0076 mmol) and KS2CN(CH2py)2 (235 mg 0063

mmol) in dicholoromethane (10 mL) was treated with a methanolic solution of NH4PF6

(206 mg 0126 mmol) and stirred at room temperature for 16 h All solvent was

removed to give a white solid which was dissolved in the minimum amount of

chloroform and filtered through Celite to give a clear filtrate The filtrate was

concentrated to approximately 1 mL and then diethyl ether (20 mL) was added to

precipitate a white product which was filtered and dried under vacuum Yield 84 mg

(96) IR (solid state) 2857 (νCminusH) 1901 1671 1594 1464 (νCminusN) 1434 1338 1302

1289 1155 1093 1068 995 (νCminusS) 816 744 cmminus1 1H NMR (CD2Cl2) 495 (s 4H

NCH2) 715 (t 2H py-H5 JHH = 77 Hz) 737-755 (m 30H+2H C6H5 + py-H3) 773

(t 2H py-H5 JHH = 77 18 Hz) 862 (m 2H py-H4) ppm 31P1H NMR (162 MHz

CD2Cl2) 148 (s PPh3 JPPt = 3290 Hz) ppm MS (FAB) mz (abundance ) = 994

(100) [M-H]+ Anal Calcd for C49H42F6N3P3PtS2 (Mw = 113812)3 C 517 H 37 N

37 Found C 497 H 37 N 35

734 [Ru(S2CN(CH2py)2)(dppm)2](PF6) (4)

A yellow solution of KS2CN(CH2py)2 (601 mg 0193 mmol) and cis-[RuCl2(dppm)2]

(1514 mg 0161 mmol) in chloroform (20 mL) was treated with a solution of NH4PF6

(525 mg 0322 mmol) in methanol (10 mL) and heated to reflux for 4 h All solvent

was removed and the resultant residue was dissolved in the minimum amount of

dichloromethane and filtered through Celite The solution was evaporated to dryness

and then triturated using ultrasound in diethyl ether (20 mL) to give a light-yellow solid

which was filtered and dried under vacuum Yield 173 mg (94) IR 3051 (νCminusH)

1590 1483 (νCminusN) 1435 1211 1097 999 (νCminusS) 835 (νPminusF) 727 695 cmminus1 1H NMR

(CDCl3) 448 491 (m x 2 2 x 2H PCH2P) 468 521 (d x 2 2 x 2H NCH2 JHH =

159 Hz) 614 (m 4H C6H5) 696 minus 766 (m 76H + 6H C6H5 + py-H3H5H6) 861(d

2H py-H4 JHH = 49 Hz) ppm 31P1H NMR (CDCl3) minus188 51 (pseudotriplet x 2

dppm JPP = 344 Hz) ppm MS (ES +ve) mz (abundance) 11442 (100) [M]+ Elem

Anal Calcd for C63H56N3P5F6RuS2 (Mw = 128921) C 587 H 44 N 33 Found

C 585 H 44 N 34

165

735 [Ru(CH=CHC6H4Me-4)(S2CN(CH2py)2)(CO)(PPh3)2] (5)

A solution of [Ru(CH=CHC6H4Me-4)Cl(BTD)(CO)(PPh3)2] (1515 mg 0161 mmol) in

chloroform (10 mL) was treated with a solution of KS2CN(CH2py)2 (60 mg 0193

mmol) in methanol (10 mL) and stirred at room temperature for 30 min All solvent was

evaporated and the residue was dissolved in the minimum amount of

dichloromethane and filtered through Celite to remove KCl All solvent was removed

again and pentane (2 times 10 mL) was added and then evaporated to ensure as much

dichloromethane as possible was removed The residue was then triturated in pentane

(10 mL) for 15 min until a brown precipitate had formed This was filtered and washed

with pentane (10 mL) and then methanol (15 mL) followed by pentane (10 mL) again

to remove BTD and dried under vacuum Yield 149 mg (89) IR 3052 (νCminusH) 1902

(νCO) 1570 1480 (νCminusN) 1434 1208 993(νCminusS) 832(νPminusF) 745 695 cmndash1 1H NMR

(CDCl3) 223 (s 3H CH3) 446 467 (s x 2 2 x 2H NCH2) 542 (dt 1H Hβ JHH =

166 Hz JHP= 34 Hz) 631 681 (AB JAB = 79 Hz 4H C6H4Me JHH = 79 Hz) 647

(d 2H py-H5 JHH = 78 Hz) 688 (d 2H py-H3 JHH = 78 Hz) 724 ndash 736 753-759

(m x 2 30H C6H5) 744 (td 2H py-H6 JHH = 78 18 Hz ) 769 (dt 2H Hα JHH =166

Hz JHP= 34 Hz) 846 (dd 2H py-H4 JHH = 166 49 Hz) ppm 31P1H NMR (CDCl3)

386 (s PPh3) ppm MS (ES +ve) mz (abundance) 1046 (100) [M+H]+ Elem Anal

Calcd for C59H52N3OP2RuS2 (Mw = 104521) C 678 H 49 N 40 Found C

677 H 48 N 41

736 [Ru(CH=CHPyr-1)(S2CN(CH2py)2)(CO)(PPh3)2] (6)

A methanolic solution of KS2CN(CH2py)2 (164 mg 0528 mmol) was treated with a

dichloromethane solution of [Ru(CH=CHPyr-1)Cl(CO)(BTD)(PPh3)2] (50 mg 0048

mmol) A solution was stirred for 3 h before all the solvent was evaporated by using

rotary evaporator The residue was dissolved in the minimum amount of chloroform

and filtered through Celite to remove KCl Solvent volume was reduced to 1 mL using

rotary evaporator and pentane (20 mL) was added and then evaporated to ensure as

much dichloromethane as possible was removed The residue was then triturated in

pentane (10 mL) for 15 min until an orange precipitate had formed This was filtered

and washed with pentane (10 mL) to remove BTD and dried under vacuum Yield 24

166

mg (43 ) IR (solid state) 2856 1910(νCO) 1668 1593(νCS) 15711475 1433 1405

1336 1289 1154 1091 937(νCS) 744 660 cm-1 1H NMR (CDCl3) 454 469 (s x

2 2 x 2H NCH2) 652 (d 2H py-H5 JHH = 79 Hz) 679 (d 1H Hβ JHH = 170 Hz

JHP = 32) 691 (t 2H py-H5 JHH = 85 Hz) 726 ndash 758 (m 30H + 2H PC6H5 + py-

H3) 762 ndash 808 (m 9H pyrenyl) 834 (dt 1H Hα JHH =170 Hz JHP= 32 Hz) 858

(dd 2H py-H3 JHH = 204 54 Hz) ppm 31P1H NMR (CDCl3) 380 (s PPh3) ppm

MS (ES +ve) mz (abundance) 1156 (45) [M + H]+ Elem Anal Calcd for

C68H53N3OP2RuS2CH2Cl2 (Mw = 115521) C 707 H 46 N 36 Found C 687 H

45 N 35

737 [Ru(C(CequivCPh)=CHPh)(S2CN(CH2py)2)(CO)(PPh3)2] (7)

A solution of [Ru(C(CequivCPh)=CHPh)Cl(CO)(PPh3)2] (100 mg 0112 mmol) in


mmol) in methanol (10 mL) and reflux for 2 h All solvent was evaporated and the

residue was dissolved in minimum dichloromethane and filtered through Celite to

remove KCl Solvent volume was reduced to 1 mL using a rotary evaporator and

pentane (20 mL) was added and then evaporated to ensure as much dichloromethane

as possible was removed The residue was then triturated in pentane (10 mL) for 15

min until a brown precipitate had formed This was filtered and washed with pentane

(10 mL) to remove BTD and dried under vacuum Yield 98 mg (77) IR 2145 (νCequivC)

1915 (νCO) 1589 1570 1475 1432 1409 1207 1157 1090 1001 750 689 cmndash1

1H NMR (CDCl3) 441 461 (s x 2 2 x 2H NCH2) 610 (s 1H Hβ) 699-742 (m

60H + 6H PC6H5 + py-H3H5H6) 756-758 (m 9H C6H5) 844 (d 2H py-H4) ppm

31P1H NMR (CDCl3) 369 (s PPh3) ppm MS (ES +ve) mz (abundance) 1132 (30)

[M + H]+ Elem Anal Calcd for C56H53N3OP2RuS2 (Mw = 113129) C 701 H 47 N

37 Found C 699 H 47 N 37

738 [Ni(S2C-N(CH2py)2)] (8)

A solution of KS2CN(CH2py)2 (33 mg 0106 mmol) and frac12 NiCl2middot6H2O (114 mg 0048

mmol) in methanol (10 mL) was stirred at room temperature for 3 h during which a

green precipitate had formed All solvent was removed and the residue was dissolved

167

in a minimum volume of chloroform and filtered through Celite The solution was

concentrated to approximately 2 mL and methanol (20 mL) was added The green

solid was filtered washed with methanol (15 mL) and hexane (10 mL) and dried under

vacuum Yield mg () IR (solid state) 1915 1589 (νCminusN) 1567 1508 1475 1429

1416 1358(νCminusH) 1237 1146 1214 1216 1147 1013 993 (νCminusS) 753 cmminus1 1H NMR

(CDCl3) 502 (s 4H NCH2) 725 (m 2H py-H5) 738 (d 2H py-H3 JHH = 78 Hz)

772 (td 2H py-H6 JHH = 78 18 Hz) 858 (m 2H py-H4) ppm MS (ES +ve) mz

(abundance ) = 607 (100) [M]+ Anal Calcd for C26H24N6NiS4 (Mw = 60745) C 514

H 40 N 138 Found C 433 H 36 N 108

739 [Ru(CH=CHC6H4Me-4)(CO)(PPh3)22(micro-dcbpy)] (9)

A solution of 22rsquo-bipyridine-44rsquo-dicarboxylic acid (100 mg 0041 mmol) and sodium

methoxide (67 mg 0123 mmol) in methanol (10 mL) was stirred at room temperature

for 30 minutes A dichloromethane (20 mL) solution of [Ru(CH=CHC6H4Mendash

4)Cl(CO)(BTD)(PPh3)2] (77 mg 0082 mmol) was added and stirred for another 2 h at

room temperature All the solvent was removed under vacuum and the crude product

was dissolved in dichloromethane (10 mL) and filtered through Celite to remove NaCl

NaOMe and excess ligand The solvent was again removed using rotary evaporator

Diethyl ether (10 mL) was added and the resulting mixture triturated in the ultrasonic

bath The dark brown precipitate obtained was filtered under vacuum washed with

diethyl ether (10 mL) and dried Yield 34 mg (47) The product can be re-crystallised

from dichloromethane-diethyl ether mixtures IR 1928 (CO) 1573(OCO) 1544 1481

1433 1185 1090 979 875 836 741 692 cmndash1 1H NMR (CDCl3) 223 (s 6H CH3)

589 (d 2H Hβ JHH = 152 Hz) 635 682 (AB 8H C6H4 JAB = 78 Hz) 692 (dd 2H

bpy JHH = 49 14 Hz) 730 ndash 743 750 (m x 2 60H C6H5) 766 (m 2H bpy) 782

(dt 2H Hα JHH = 152 Hz JHP = 27) 846 (d 2H bpy JHH = 49) ppm 31P1H NMR

(CDCl3) 382 (s PPh3) ppm MS (ES +ve) mz (abundance) 1894 (4)

[M+4Na+H2O]+ 1543 (3) [MndashPPh3+Na]+ 1113 (50) [MndashvinylndashCOndash2PPh3]+ 991 (100)

[MndashCOndash3PPh3+Na]+ Elem Anal Calcd for C104H84N2O6P4Ru2middot25CH2Cl2 (MW =

199616) C 641 H 45 N 14 Found C 637 H 42 N 18

168

7310 [Ru(C(CequivCPh)=CHPh)(CO)(PPh3)22 (micro-dcbpy)] (10)

A methanolic solution (10 ml) of 22rsquo-bipyridine-44rsquo-dicarboxylic acid (20 mg 0082

mmol) and sodium methoxide (133 mg 0246 mmol) was stirred for 30 minutes at

room temperature and treated with a dichloromethane solution (10 mL) of

[Ru(C(CequivCPh)=CHPh)Cl(CO)(PPh3)2] (1463 mg 0164 mmol) The reaction was

stirred for 2 h at room temperature The solvent was removed under vacuum (rotary

evaporator) and the resulting red product was dissolved in the minimum amount of

dichloromethane This was filtered through Celite and the solvent removed by rotary

evaporation Diethyl ether (10 mL) was added and subsequent ultrasonic titruration

provided a dark red precipitate which was filtered washed with diethyl ether (10 mL)

and dried Yield 80 mg (50) The product is slightly soluble in diethyl ether IR 2163

(CequivC) 1929 (CO) 1522 (OCO) 1482 1432 1186 1094 877 743 691 cmndash1 1H NMR

(CDCl3) 579 (s(br) 2H Hβ) 692 (dd 2H bpy JHH = 62) 700 (m 6H C6H5) 709

(t 6H CC6H5 JHH = 75 Hz) 720 - 722 (m 34H PC6H5) 735 (m 4H CC6H5) 742

(t 4H CC6H5 JHH = 75 Hz) 754 - 759 (m 26H PC6H5) 778 (m 2H bpy) 846 (dd

2H bpy) ppm 31P1H NMR (CDCl3) 382 (s PPh3) ppm MS (ES +ve) mz

(abundance) 1980 (10) [M+H+Na]+ 897 (100) [Mndash4PPh3ndashCO+H2O]+ Elem Anal

Calcd for C118H88N2O6P4Ru2 (MW = 195601) C 724 H 45 N 14 Found C 723

H 43 N 16

7311 [Ru(dppm)22(micro-dcbpy)] (PF6)2 (11)


methoxide (89 mg 0164 mmol) in methanol (10 mL) was stirred for 30 minutes at

room temperature A solution of cis-[RuCl2(dppm)2] (77 mg 0082 mmol) in

dichloromethane (20 mL) was then added along with ammonium hexafluorophosphate

(226 mg 0123 mmol) The reaction mixture was stirred for 2 h at room temperature

All the solvent was then removed using a rotary evaporator and the crude product was

re-dissolved in dichloromethane (10 mL) and filtered through Celite Ethanol (20 mL)

was added and the solvent volume slowly reduced on a rotary evaporator until the

formation of a brown solid The precipitate was filtered washed with petroleum ether

(10 mL) and dried under vacuum The product is partially soluble in ethanol

contributing to a reduced yield Yield 48 mg (51) IR 1593 1521 (OCO) 1482 1426

169

1186 1093 835 (PF) cmndash1 1H NMR (CDCl3) 416 476 (m x 2 2 x 4H PCH2P)

626 (m 8H C6H5) 699 minus 754 (m 56H + 2H C6H5 + bpy) 765 780 (m x 2 2 x 8H

C6H5) 855 (s 2H bpy) 891 (d 2H bpy JHH = 43 Hz) ppm 31P1H NMR (CDCl3)

minus119 87 (pseudotriplet x 2 dppm JPP = 388 Hz) ppm MS (MALDI +ve) mz

(abundance) 2128 (12) [M+H+PF6]+ 1981 (11) [M+H]+ Elem Anal Calcd for

C112H94F12N2O4P10Ru2middotCH2Cl2 (MW = 235675) C 576 H 41 N 12 Found C 573

H 42 N 10

7312 [Ru(dppm)22(micro-dcbpy)] (BPh4)2 (12)

Employing the same protocols as used for the synthesis of 11 A solution of H2dcbpy

(100 mg 0041 mmol)sodium methoxide (89 mg 0164 mmol) cis-[RuCl2(dppm)2]

(77 mg 0082 mmol and sodium tetraphenylborate (561 mg 0164 mmol) provided

a brown solid The precipitate was filtered washed with petroleum ether (10 mL) and

dried under vacuum Yield 48 mg (46) IR 1579 1509(OCO) 1481 1426 1310

1264 1187 1092 999 729 cmndash1 1H NMR (CDCl3) 393 456 (m x 2 2 x 4H

PCH2P) 611 (m 8H C6H5) 681 minus 765 (m 56H + 2H C6H5 + bpy) 851 (s 2H bpy)

880 (d 2H bipy JHH = 49 Hz) ppm 31P1H NMR (CDCl3) minus116 88 (pseudotriplet

x 2 dppm JPP = 392 Hz) MS (ES +ve) mz (abundance) 991 (90) [M2]+ Elem Anal

Calcd for C160H134B2N2O4P8Ru2 (Mw = 262039) C 733 H 52 N 11 Found C

715 H 51 N 10

7313 [ReCl(CO)3(micro-H2dcbpy)]23 (13)

Re(CO)5Cl (193 mg 053 mmol) was dissolved in an hot toluene (50 mL) and

methanol (20 mL) 44rsquo-dicarboxylic-22rsquo-bipyridine (130 mg 053 mmol) was added to

the solution and the reaction mixture was stirred under reflux for 1 h During this time

the colour of the solution changed from colourless to orange The solution was kept at

ndash20 degrees for 1 h to precipitate the unreacted starting material which was then

filtered The resulting orange solution was evaporated to dryness to yield the product

Yield 233 mg (80 ) IR 2030 (CO) 1902 (CO) 1875 (CO) 1734 1511 (OCO) 1426

1214 1095 832 772 731 691 663 cmndash1 1H NMR (d6-DMSO) 814 (dd 2H bpy

JHH = 57 17 Hz) 915 (dd 2H bpy JHH = 17 08 Hz) 922 (dd 2H bpy JHH = 57

170

08 Hz) 1439 (s(br) 2H CO2H) ppm The data obtained were found to be in good

agreement with those reported in the literature23


A solution of 13 (30 mg 0055 mmol) and sodium methoxide (119 mg 022 mmol) in

methanol (10 mL) was stirred for 30 min at room temperature A solution of

[Ru(CH=CHC6H4Mendash4)Cl(CO)(BTD)(PPh3)2] (1027 mg 0109 mmol) in

dichloromethane (10 mL) was added and stirred for another 2 h Ethanol (10 mL) was

added and the solvent volume slowly reduced on a rotary evaporator until the

formation of a brown solid was complete The precipitate was filtered washed with

ethanol (10 mL) and dried under vacuum Yield 79 mg (69 ) IR 2019 (CO) 1918

(CO) 1890 (CO) 1531 (OCO) 1481 1433 1391 1184 1090 979 827 743 692 cmndash

1 1H NMR (CDCl3) 223 (s 6H CH3) 594 (d 2H Hβ JHH = 150 Hz) 638 682

(AB 8H C6H4 JAB = 77 Hz) 701 (dd 2H bpy JHH = 56 14 Hz) 726 (m 2H bpy)

736 752 (m x 2 60H C6H5) 784 (dt 2H Hα JHH = 150 Hz JHP = 28 Hz) 868 (d

2H bpy JHH = 56 Hz) ppm 13C1H NMR (CD2Cl2) 2064 (t RuCO JPC = 150 Hz)

1978 (s 2 x ReCO) 1976 (s ReCO) 1728 (s CO2) 1551 1526 (s x 2 2 x bpy)

1510 (t C JPC = 115 Hz) 1424 (s bpy) 1380 (s ipsop-C6H4) 1347 (tv om-C6H5

JPC = 54 Hz) 1337 (s C) 1322 (s ipsop-C6H4) 1311 (tv ipso-C6H5 JPC = 220

Hz) 1307 (s p-C6H5) 1287 (tv om-C6H5 JPC = 55 Hz) 1284 (s om-C6H4) 125 (s

bpy) 1246 (s om-C6H4) 1215 (s bpy) 210 (s p-C6H4) ppm 31P1H NMR (CDCl3)

381 (s PPh3) ppm MS (ES +ve) mz (abundance) 1244 (12) [Mndash3PPh3ndash

3CO+H+Na]+ 1303 (4) [Mndash3PPh3]+ Elem Anal Calcd for C107H84N2O9P4ReRu2 (MW

= 208951) C 615 H 41 N 13 Found C 614 H 39 N 14



methanol (10 ml) was stirred for 30 min at room temperature A brown solution of

[Ru(C(CequivCPh)=CHPh)Cl(CO)(PPh3)2] (973 mg 0109 mmol) in dichloromethane (10

mL) was added and stirred for another 2 h Ethanol (10 mL) was added and the solvent

volume slowly reduced on a rotary evaporator until the formation of a brown solid was

complete The precipitate was filtered washed with ethanol (10 mL) and dried under

171

vacuum Yield 82 mg (66 ) IR 2019 (CO) 1919 (CO) 1890 (CO) 1531 (OCO)

1481 1433 1185 1094 826 743 691 cmndash1 1H NMR (CDCl3) 612 (s(br) 2H Hβ)

689 (d 2H bpy JHH = 56 Hz) 704 (m 6H CC6H5) 712 (t 6H CC6H5 JHH = 74

Hz) 721 - 735 (m 36H PC6H5) 739 -746 (m 8H CC6H5) 759 (m 24H + 2H

PC6H5 + bpy) 866 (d 2H bpy JHH = 56 Hz) ppm 31P1H NMR (CDCl3) 379 (s

PPh3) ppm MS (ES +ve) mz (abundance) 1245 (4) [Mndash3PPh3ndashCOndashenynyl]+ 898

(100) [(MndashPPh3ndashenynyl)2]+ Elem Anal Calcd for C121H88ClN2O9P4ReRu2 (MW =

226170) C 643 H 39 N 12 Found C 641 H 38 N 12

7316 [Ru(dppm)22 (micro-[Re(dcbpy)(CO)3Cl])] (PF6)2 (16)

An orange solution of 13 (30 mg 0055 mmol) and sodium methoxide (119 mg 022

mmol) in methanol (10 mL) was stirred for 30 min at room temperature A yellow

solution of cis-[RuCl2(dppm)2] (1025 mg 011 mmol) in dichloromethane (10 mL) was

added to the mixture leading to an immediate colour change to orange Potassium

hexafluorophosphate (405 mg 022 mmol) was added and the reaction mixture was

stirred for another 1 h at room temperature All the solvent was removed under vacuum

and the crude product was dissolved in dichloromethane (10 mL) and filtered through

Celite to remove NaCl NaOMe and excess ligand Ethanol (10 mL) was added and

the solvent volume was slowly reduced on a rotary evaporator until the formation of

an orange solid The precipitate was filtered washed with ethanol (10 mL) and dried

under vacuum Yield 85 mg (60) IR 2020 (CO) 1919 (CO) 1892 (CO) 1515 (C-

O) 1482 1434 1092 839 741 692 cmndash1 1H NMR (CD2Cl2) 425 480 (m x 2 2 x

4H PCH2P) 628 (m 8H C6H5) 703 minus 793 (m 72H + 2H C6H5 + bpy) 792 (d 2H

bpy JHH = 89 Hz) 918 (dd 2H bpy JHH = 112 52 Hz) ppm 31P1H NMR (CD2Cl2)

minus115 93 (pseudotriplet x 2 dppm JPP = 389 Hz) ppm MS (ES +ve) mz

(abundance) 1144 (100) [M2]+ Elem Anal Calcd for

C115H94ClF12N2O7P10ReRu2middot2CH2Cl2 (MW = 274737) C 511 H 36 N 10 Found

C 509 H 33 N 13

172

7317 (SC6H4CO2H-4)2 (17)

A solution of iodine (1M in MeOH) was added dropwise to a colourless solution of 4-

mercaptobenzoic acid (450 mg 2919 mmol) in MeOH (60 mL) until the mixture took

on a persistent orange colouration The cloudy mixture was stirred for a further 30

minutes and then filtered The resulting white solid was washed several times with

ethanol and dried under vacuum overnight Yield 400 mg (90) IR (solid state) 2838

2669 2552 1676 (VCO) 1591 1423 1323 1292 1181 1116 933 850 cmndash1 1H NMR

NMR (d6-DMSO) 752 781 (d x 2 2 x 4 H JHH = 80 Hz C6H4) ppm The CO2H

protons were not observed These data agree well with literature values1824

7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18)

A solution of cis-[RuCl2(dppm)2] (263 mg 0280 mmol) in dichloromethane (50 mL)

was treated with a solution of 1 (43 mg 0140 mmol) sodium methoxide (30 mg 0555

mmol) and ammonium hexafluorophosphate (91 mg 0558 mmol) in methanol (25

mL) The reaction mixture was stirred for 2 h at room temperature All solvent was

removed under vacuum and the crude product was dissolved in dichloromethane (10

mL) and filtered through Celite to remove NaCl NaOMe and excess ligand Ethanol

(20 mL) was added and the solvent volume was slowly reduced on a rotary evaporator

until the precipitation of the yellow solid was complete This was filtered washed with

petroleum ether (10 mL) and dried under vacuum Yield 281 mg (86) IR (solid

state) 3058 1590 (νCO) 1484 1426 1189 1097 834 (νPF)cmminus1 1H NMR

(dichloromethane-d2) δ 395 463 (m times 2 2 times 4H PCH2P) 618 (m 8H C6H5)

692minus776 (m 72H + 8H C6H5 +C6H4) ppm 31P1H NMR NMR (d6-DMSO) δ minus120

89 (pseudotriplet times 2 JPP = 390 Hz dppm) ppm 1H NMR (d6-DMSO) δ 388 505

(m times 2 2 times 4H PCH2P) 614 (m 8H C6H5) 686minus777 (m 72H + 8H C6H5 +C6H4)

ppm 13C1H NMR (CD2Cl2 500 MHz) δ = 1817 (s CO2) 1419 (s CS) 1349 (s

CCO2) 1338 1324 1321 (m times 3 C6H5) 1317 (s om-C6H4) 1313 (m C6H5) 1311

1308 (s times 2 C6H5) 1304 (s om-C6H4) 1296 1294 1293 1288 (m times 4 C6H5)

1264 1262 (s times 2 C6H5) 436 (t JPC = 115 Hz PCH2P) ppm 31P1H NMR (d6-

DMSO) δ minus127 93 (pseudotriplet times 2 JPP = 391 Hz dppm) ppm MS (FAB + ve)

mz () 2044 (5) [M]+ Anal Calcd for C114H96F12O4P10Ru2S2 (Mw = 233397) C 587

H 42 Found C 586 H 42

173

7319 [AuSC6H4CO2Ru(dppm)22]PF6 (19)

A solution of cisndash[RuCl2(dppm)2] (55 mg 0059 mmol) in dichloromethane (10 mL) was

added to [N(PPh3)2][Au(SC6H2CO2H)2] (30 mg 0029 mmol) ammonium

hexafluorophosphate (19 mg 0117 mmol) and sodium methoxide (60 mg 0111

mmol) in mixture of methanol (5 mL) and dichloromethane (2 mL) The reaction

mixture was stirred for 2 h at room temperature All solvent was removed under

vacuum and the crude product was dissolved in dichloromethane (10 mL) and filtered

through Celite to remove NaCl NaOMe and excess ligand Ethanol (20 mL) was

added and the solvent volume was slowly reduced on a rotary evaporator until the

precipitation of the yellow product was complete This was filtered washed with cold

ethanol (5 mL) petroleum ether (10 mL) and dried under vacuum Yield 49 mg (71)

IR (solid state) 1590 (νC-O) 1484 1426 1312 1261 1177 1094 1027 1014 1000

834 (νPF) cmndash1 1H NMR (d6-DMSO) 388 (m 2 x 2H PCH2P) 505 (m 2 x 2H

PCH2P) 612 (m 8H C6H5) 686 minus 775 (m 72H + 8H C6H5 + C6H4) ppm 31P1H

NMR (d6ndashDMSO) minus794 (pseudotriplet JPP = 390 Hz dppm) 1402 (pseudotriplet

JPP = 390 Hz dppm) ppm MS (ES +ve) mz () 2044 (100) [M ndash Au]+ Anal Calcd

() for C114H96AuF6O4P9Ru2S2 (Mw = 238597) C 574 H 41 Found C 572 H 40


A solution of [Au(SC6H4CO2H)(PPh3)] (15 mg 0025 mmol) and sodium methoxide

(14 mg 0026 mmol) in dichloromethane (5 ml) and methanol (2 ml) was added

dropwise to a stirred solution of [Ru(CH=CHC6H4Mendash4)Cl(CO)(BTD)(PPh3)2] (23 mg

0025 mmol) in dichloromethane (10 mL) After stirring for 4 h all solvent was removed

under vacuum The residue was dissolved in dicholoromethane (10 ml) and filtered

through celite to remove inorganic salts The solvent was removed and the resulting

yellow solid was washed with diethyl ether (10 mL) This was dried under vacuum

Yield 22 mg (64) IR (solid state) 1908 (νCO) 1586 (νCO) 1481 1425 1175 1095

863 742 692 cmndash1 1H NMR (CD2Cl2) 223 (s 3H CH3) 583 (d JHH = 154 1H

Hβ) 639 683 (d x 2 JHH = 80 Hz 4H C6H4Me) 685 720 (d x 2 JHH = 83 Hz 4H

SC6H4) 732 ndash 740 746 ndash 763 (m x 2 45H C6H5) 785 (dt JHH = 154 JHP = 26 Hz

1H Hα) ppm 13C1H NMR (CD2Cl2 500 MHz) δ 2071 (t JPC = 153 Hz CO) 1782

174

(s CO2) 1535 (t JPC = 117 Hz Cα) 1476 (s CS) 1386 (s C14-C6H4) 1347 (tv

JPC = 58 Hz om-RuPC6H5) 1345 (d JPC = 137 Hz om-AuPC6H5) 1338 (t(br) JPC

unresolved Cβ) 1333 (s C14-C6H4) 1322 (s p- AuPC6H5) 1319 (tv JPC = 214 Hz

ipso-RuPC6H5) 1307 (s om-C6H4) 1305 (s C14-C6H4) 1301 (s p-RuPC6H5) 1297

(d JPC = 112 Hz om-AuPC6H5) 1293 (d JPC = 253 Hz ipso-AuPC6H5) 1286 (s

om-C6H4) 1283 (tv JPC = 56 Hz om-RuPC6H5) 1279 1245 (s times 2 om-C6H4)

209 (sCH3) ppm 31P1H NMR (CD2Cl2) 375 (s RuPPh3) 387 (s AuPPh3) MS

(ES +ve) mz () 1481 (5) [M + Na + K]+ Anal Calcd () for C71H58AuO3P3RuS (Mw

= 138224) C 617 H 42 Found C 617 H 41


Employing the same protocols as used for the synthesis of 20 with

[Au(SC6H4CO2H)(PPh3)] (35 mg 0057 mmol) sodium methoxide (31 mg 0057

mmol) and [Ru(C(CequivCPh)=CHPh)(CO)(PPh3)2] (50 mg 0057 mmol) provided a

yellow solid Yield 57 mg (68) IR (solid state) 2163 (νCequivC) 1919 (νCO) 1588 (νCO)

1481 1433 1419 1173 1094 864 742 690 cmndash1 1H NMR (CD2Cl2) 608 (s(br)

1H CHPh) 686 (d JHH = 81 Hz 2H C6H4Me) 700 710 717 ndash 772 (m x 3 42H

C6H4Me + CC6H5 + PC6H5) ppm 13C1H NMR (CD2Cl2 500 MHz) δ 2074 (t JPC =

150 Hz CO) 1780 (s CO2) 1476 (s CS) 1404 (t(br) JPC unresolved Cα) 1349

(tv JPC = 59 Hz om-RuPC6H5) 1345 (d JPC = 136 Hz om-AuPC6H5) 1322 (s p-

AuPC6H5) 1317 (s om- C6H4) 1312 (tv JPC = 216 Hz ipso-RuPC6H5) 1306 (s

om-C6H4) 1301 (s p-RuPC6H5) 1297 (d JPC = 257 Hz ipso-AuPC6H5) 1296 (d

JPC = 112 Hz om-AuPC6H5) 1289 (s quaternary-C) 1285 (s CC6H5) 1281 (tv

JPC = 50 Hz om-RuPC6H5) 1278 1274 (s times 2 CC6H5) 1273 (s quaternary-C)

1266 (t(br) JPC unresolved Cβ) 1249 (s CC6H5) ppm 31P1H NMR (CD2Cl2) 375

(s RuPPh3) 371 (s AuPPh3) MS (ES +ve) mz () 1469 (6) [M]+ Anal Calcd ()

for C78H60AuO3P3RuS (Mw = 146833) C 638 H 41 Found C 637 H 40

175

7322 [(Ph3P)Au(SC6H4CO2-4)RuCH=CbpyReCl(CO)3((PPh3)2] (22)

Employing the same protocol used to synthesize 20 with [Au(SC6H4CO2H)(PPh3)] (23

mg 0038 mmol) sodium methoxide (21 mg 0039 mmol) and [RuCH=CH-

bpyReCl(CO)3Cl(CO)(BTD)(PPh3)2] (50 mg 0038 mmol) provided an orange solid

Yield 61 mg (92) IR (solid state) 2016 (νCO) 1909 (νCO) 1885 (νCO) 1587 (νCO)

1535 1481 1434 1419 1176 1095 862 744 692 cm-1 1H NMR (CD2Cl2) 578 (d

JHH = 156 Hz 1H Hβ) 692 (AB JAB = 85 Hz 2H SC6H4) 696 (dd JHH = 86 20

Hz 1H bpy) 721 (AB JAB = 85 Hz 2H SC6H4) 736 ndash 761 (m 45H C6H5) 778 (d

JHH = 85 Hz 2H bpy) 792 (s(br) 1H bpy) 801 (m 2H bpy) 892 (dt JHH = 156

Hz JHH = 25 Hz 1H Hα) 896 (d JHH = 54 Hz 1H bpy) ppm 31P1H NMR (CD2Cl2)

379 (s RuPPh3) 380 (s AuPPh3) MS (ES +ve) mz () 1753 (22) [M]+ 1793 (62)

[M + H + K]+ Anal Calcd () for C77H58AuClN2O6P3ReRuS (Mw = 175198) C 528

H 33 N 16 Found C 526 H 34 N 17

7323 Au29[SC6H4CO2Ru(dppm)2]PF6 (NP1)

A solution of tetracholoroauric acid trihydrate (50 mg 0127 mmol) in methanol (10

mL) was added to a solution of 18 (1494 mg 0064 mmol) in methanol (5 mL) The

mixture was stirred for 30 min at room temperature and then cooled to 4 degC A fresh

solution of sodium borohydride (404 mg 1063 mmol) in water (3 mL) was then added

dropwise The colour of the solution changed from yellow to dark brown indicating the

formation of nanoparticles The mixture was stirred for a further 3 h at 10 degC The

supernatant was removed by centrifugation and the brown solid was washed with

water (3 x 10 mL) and dichloromethane (10 mL) to remove unattached surface units

The black nanoparticles (40 mg) were dried under vacuum and stored under nitrogen

IR (solid state) 1575 (νC-O) 1483 1435 1096 999 817 (νPF) 724 685 cm-1 1H NMR

(d6-DMSO 500 MHz) 444 576 (m x 2 2 x 2H PCH2P) 659 (m 4H C6H5) 708

724 737 753 770 793 (m x 6 36 H + 4 H C6H5 + C6H4) ppm 31P1H NMR (d6-

DMSO 500 MHz) minus186 minus32 (pseudoquartet x 2 JPP = 357 Hz dppm) ppm TEM

Analysis of over 200 nanoparticles gave a size of 29plusmn02 nm EDS Confirmed the

presence of gold and ruthenium and indicated the presence of sulfur phosphorus

oxygen and fluorine TGA 378 surface units 622 gold and ruthenium

(Au84(SC6H4CO2Ru(dppm)2)PF6)

176


Tetrachloroauric acid trihydrate (20 mg 0051 mmol) was dissolved in ultrapure water

(60 mL) The solution was heated to reflux for 20 min A pre-heated aqueous solution

(4 mL) of trisodium citrate (527 mg 0204 mmol) was added The heating source was

quickly removed and the stirred solution was left to cool to room temperature A

mixture of methanol and acetonitrile solution (3 mL) of 18 (1786 mg 0077 mmol) was

added and the mixture stirred for 3 h at room temperature after which it was stored at

4 degC overnight to allow the nanoparticles formed to settle The supernatant was

removed and the nanoparticles were washed with water (3 x 10 mL) and centrifuged

Methanol (3 x 10 mL) and dichloromethane (10 mL) washes were employed to remove

unattached surface units The resulting dark blue solid (112 mg) isolated was dried

under vacuum and stored under nitrogen IR (solid state) 1586 (νC-O) 1485 1436

1098 1000 834 (νPF) 735 698 cm-1 1H NMR (d6-DMSO 500 MHz) 443 574 (m

x 2 2 x 2H PCH2P) 661 (m 4H C6H5) 710 726 738 754 772 794 (m x 6 36H

+ 4H C6H5 + C6H4) ppm 31P1H NMR (d6-DMSO 500 MHz) minus186 minus32

(pseudotriplet x 2 JPP = 356 Hz dppm) ppm TEM Analysis of over 200 nanoparticles

gave a size of 119 plusmn 09 nm EDS Confirmed the presence of gold and ruthenium

and indicated the presence of sulfur phosphorus oxygen and fluorine TGA 425

surface units 575 gold and ruthenium (Au68(SC6H4CO2Ru(dppm)2)PF6)

7325 Pd[SC6H4CO2Ru(dppm)2]PF6 (NP3)

[PdCl2(NCMe)2] (13 mg 0050 mmol) and tetraoctylammonium bromide (1094 mg

0200 mmol) were dissolved in dry tetrahydrofuran (10 mL) under an inert atmosphere

After 10 min stirring lithium triethylborohydride (1 M tetrahydrofuran solution 015 mL

3 eq) was added with vigorous stirring The solution faded from red to black indicating

the formation of nanoparticles After 30 min a solution of 18 (1166 mg 0050 mmol)

in a 21 mixture of dry tetrahydrofuran and dry acetonitrile was added (3 mL) The

mixture was stirred overnight at room temperature The mixture was then centrifuged

and the supernatant removed The remaining solid was washed with methanol (2 x 10

mL) and acetone (2 x 10 mL) The resultant black solid (165 mg) was dried under

vacuum and stored under nitrogen It was found to be insoluble in all available

deuterated solvents so no NMR data could be recorded IR (solid state) 1585 (νC-O)

177

1485 1435 1098 828 (νPF) cm-1 TEM Analysis of over 200 nanoparticles gave a

size of 22plusmn02 nm EDS Confirmed the presence of palladium and ruthenium and

indicated the presence of sulfur phosphorus oxygen and fluorine TGA 384

surface units 616 palladium and ruthenium (Pd151(SC6H4CO2Ru(dppm)2)PF6)

178


741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 925

NaS2CNEt2 (106 mg 0047 mmol) was dissolved in methanol (10 mL) and stirred for

10 min A dichloromethane solution (20 mL) of cis-[PdCl2(PPh3)2] (300 mg 0043

mmol) was added to the reaction mixture It was followed by the addition of a

methanolic solution (10 mL) of KPF6 (317 mg 0172 mmol) The reaction mixture was

reflux for 5 h and then all the solvent was removed under reduced pressure The

precipitate was dissolved in dichloromethane (10 mL) and filtered through Celite to

remove any excess KCl Then the solvent again was removed under reduced

pressure and the resulting precipitate was titrurated in the presence of diethyl ether

(20 mL) in an ultrasonic bath The yellow product was filtered washed with diethyl

ether and dried Yield 36 mg (91) 1H NMR (CDCl3) 130 (t 6H JHH= 72 CH3)

360 (q 12H JHH= 72 CH2) 730-749 (m 30H PPh3) ppm 31P1H NMR (CDCl3)

304 (s PPh3) The data obtained were in agreement with literature925

742 [Pd(S2CNEt2)2] (24)26

K2PdCl4 (100 mg 0306 mmol) was added to a methanolic solution of NaS2CNEt2

(10481 mg 0612 mmol) and the mixture stirred for 1 h at room temperature to

produce a yellow precipitate The product was isolated by filtration and washed with

MeOH (2 x 5 mL) and water (2 x 5 mL) and again MeOH (5 mL) and dried Yield 320

mg (85 )1H NMR (CDCl3) 130 (t 12H JHH = 72 CH3) 373 (q 12H JHH = 72

CH2) ppm 13C1H NMR (CDCl3) 124 (s CH3) 440 (s CH2) 210 (s CS2) The

data obtained were in agreement with literature2627

743 [(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25)

KS2CNC4H8NCS2K (337 mg 0107 mmol) was dissolved in methanol (10 mL) and

stirred for 10 min A dichloromethane solution (20 mL) of cis-[PdCl2(PPh3)2] (1500 mg

0214 mmol) was added followed by a methanolic solution (10 mL) of KPF6 (788 mg

0428 mmol) The reaction was stirred at reflux for 5 h and then all the solvent removed

179

under reduced pressure (rotary evaporation) The residue was dissolved in

dichloromethane (10 mL) and filtered through diatomaceous earth (Celite) to remove

inorganic salts After all solvent had been removed diethyl ether (20 mL) was added

and the solid triturated in an ultrasonic bath The resulting orange precipitate was

filtered washed with diethyl ether (20 mL) and dried under vacuum Yield 151 mg

(79) IR (ATR) 1514 1480 1434 1280 1239 1094 999 (νC-S) 831 (νPF) cm-1 1H

NMR (CD2Cl2) 392 (s NC4H8N 8H) 732-752 (m C6H5 60H) ppm 13C1H NMR

(CD2Cl2) 448 (s NC4H8N) 1290 (tv om-C6H5 JPC = 55 Hz) 1306 (s p-C6H5)

1341 (obscured ipso-C6H5) 1341 (tv om-C6H5 JPC = 60 Hz) 2060 (s CS2) ppm

31P1H NMR (CD2Cl2) 305 (s PPh3) ppm MS (ES) mz (abundance ) 749 (100)

[M2 + 3MeCN + 2H]+ Elemental analysis Calculated for C78H68F12N2P6Pd2S4 C

524 H 38 N 16 Found C 525 H 37 N 16

744 [(Ph3P)2PdS2CN(CH2Ph)CH2CH2N(CH2Ph)CS2Pd(PPh3)2][PF6]2 (26)

KS2CN(Bz)CH2CH2N(Bz)CS2K (502 mg 0107 mmol) was dissolved in methanol (10

mL) and stirred for 10 min A dichloromethane solution (20 mL) of cis-[PdCl2(PPh3)2]

(1500 mg 0214 mmol) was added followed by a methanolic solution (10 mL) of KPF6

(788 mg 0428 mmol) The reaction was stirred at reflux for 6 h and then all the

solvent was removed under reduced pressure (rotary evaporation) The residue was

dissolved in a minimum volume of dichloromethane (10 mL) and filtered through

diatomaceous earth (Celite) After the solvent had been removed diethyl ether (20

mL) was added and the solid triturated in an ultrasonic bath The resulting yellow

precipitate was filtered washed with diethyl ether (20 mL) and dried Yield 174 mg

(84) IR (ATR) 1504 1481 1434 1229 1094 999 (νC-S) 831 (νPF) cm-1 1H NMR

(CD2Cl2) 362 (s 4H NCH2CH2N) 456 (s 4H CH2Ph) 694 (d 4H ortho-C6H5

JHH = 76 Hz) 717 (t 4H meta-C6H5 JHH = 76 Hz) 727 (t 2H para-C6H5 JHH = 72

Hz) 731 - 756 (m 60H PPh3) ppm 13C1H NMR (CD2Cl2) 451 539 (s x 2 NCH2

and PhCH2) 1288 (s om-C6H5) 1289 1290 (s(br) x 2 om-PC6H5) 1291 (s om-

C6H5) 1295 (s p-C6H5) 1319 (s(br) x 2 p-PC6H5) 1326 (s ipso-C6H5) 1341

(obscured ipso-PC6H5) 1341 1342 (s(br) x 2 om-C6H5) 2068 (s CS2) ppm

31P1H NMR (CD2Cl2) 305 309 (d x 2 PPh3 Jpp = 325 Hz) ppm MS (ES) mz

(abundance) 826 (100) [M2 + H]+ Elemental analysis Calculated for

180

C90H78F12N2P6Pd2S4 C 557 H 41 N 14 Found C 557 H 39 N 15

745 [Pd(Me2dazdt)2]I6 (27)

NNrsquo-dimethyl-perhydrodiazepine-23-dithione diiodide adduct (Me2dazdt2I2) (2782

mg 040 mmol) and Pd powder (212 mg 020 mmol) was dissolved in acetone (100

mL) The reaction mixture was stirred until all the palladium dissolves (about 10 mg of

Pd powder dissolves in 2 h) The solution was reduced to 25 mL by using rotary

evaporator and solvent diffusion technique (diethyl ether into acetone) was employed

to form a flat black crystal of the product Yield 229 mg (92) IR (ATR) 1538 1457

1429 1393 1357 1330 1287 1283 1107 1073 1028 981 825 743610 581 532

cm-1 1H NMR (d6-DMSO) 248 (m 1H CCH2C) 373 (s 6H NCH3) 402 (t 4H

NCH2 JHH = 67 Hz)

746 [PdI2(Me2dazdt)] (28)

[PdI2(Me2dazdt)] can be obtained as the by-product in the synthesis of 27 by second

diffusion re-crystallisation with Et2O At a smaller scale of Pd powder (00106 g 010

mmol) used small black crystals (00031 g 00057 mmol 57) was collected 28

was obtained as precipitate by addition of Me2dazdt (01053 g 056 mmol) palladium

(00600 g 056 mmol) and iodine (01431 g 056 mmol) to acetone (60 mL) 28 was

retrieved by filtration as black powder (03086 g 051 mmol 91) Data were found

to be in good agreement with literature values28 IR (ATR) 2986 1700 (acetone)

1527 1460 1423 1395 1359 1330 1286 1264 1223 1114 1073 1027 958 897

825 744 cm-1 1H NMR (d6-DMSO) 242 (m 2H CCH2C) 360 (s 6H NCH3) 384

(t4H NCH2 JHH = 67 Hz) Data was found to be in a good agreement with the

literature28

747 [Pd(Cy2DTO)2]I8 (29)

A mixture of NNrsquo-dicyclohexyl-dithiooxamide (535 mg 0188 mmol) and palladium

powder (100 mg 0094 mmol) in ethyl acetate (30 mL) was treated with iodine (1193

mg 0470 mmol) in ethyl acetate (20 mL) The mixture was stirred at room temperature

for 6 h Concentration of the solvent volume and layering with diethyl ether led to a red-brown

181

microcrystalline product ([29]I8) which was filtered washed with diethyl ether (2 x 20

mL) and dried Yield 111 mg (70) IR (ATR) 3207 3085 3015 2934 2851 1556

1423 1364 1201 1174 658m cm-1 1H NMR (d6-DMSO) 120 (t 1H JHH = 126 Hz)

135 (q 2H JHH = 126 Hz) 150 (s 2H) 163 (d 1H JHH = 126 Hz) 176 (d 2H JHH

= 138 Hz) 182 (m 2H) 394 (d 1H JHH = 109 Hz) MS (ES) mz (abundance )

726 (100) [M + H2O + MeOH]+ Elemental analysis Calculated for PdC28S4N4H48I8 C

199 H 29 N 33 Found C 203 H 28 N 34

748 General set up for catalysis

The design of the catalysis setup depends on the temperature For the reactions at 50

degC below the boiling point of the solvent commercially available 14 mL thin glass vials

were used For reactions at 100 degC above the boiling point of the solvent thick-

walled vials sealed with a screw cap lined with Teflon and a blast shield were used for

safety purposes because of the pressure built up in the reaction In both cases the

vials were heated in a drysyn multiwell heating block The minimum volume of silicone

oil was added to the wells to guarantee homogenous heating and efficient heat transfer

between the block and the vials An electronic contact thermometer attached to the

magnetic stirrer hotplate was employed to regulate the temperature of the reaction An

independent thermometer was installed to monitor inconsistencies of temperature in

the reaction The designated temperature was allowed to be reached before the vials

were inserted into the wells for the reaction to proceed All the reactions were

performed at least three times and yields were determined by 1H NMR based on

average of three independent experiments to improve the reliability of the catalytic

data

182

Reaction set up for catalytic reactions

7481 Reaction A Synthesis of 10-alkoxybenzo[h]quinoline

In small-scale experiments benzo[h]quinoline (500 mg 028 mmol)

(diacetoxyiodo)benzene (1804 mg 056 mmol) and the selected catalyst (loadings

183

between 1 - 5 mol) were treated in the alcohol (25 mL) The reaction mixture was

heated in a glass vial (50 or 100 degC) and stirred using a small magnetic stir bar for a

designated time frame [Pd-dithioxamides catalyst (1 2 3 4 and 5 h) Pd-

dithiocarbamates (2 4 6 and 24 h)] The solvent was removed under reduced

pressure to yield a yellow crude oil which was dissolved in deuterated chloroform and

analysed by 1H NMR The yield of product was determined by comparing the

integration of resonances of H-2 (930 ppm) and H-10 protons (901 ppm) of

benzo[h]quinoline with the diagnostic resonance of methoxy (CH3) ethoxy (CH2CH3)

trifluoroethoxy (CH2CF3) which appeared at 419 163 and 445 and 474 ppm

respectively in the alkoxy product A mixture of isopropanol (125 mL) and glacial

acetic acid (125 mL) was employed to prepare 10-isopropoxybenzo[h]quinoline29

An isolated yield experiment was carried out on a larger scale of benzo[h]quinoline

(150 mg) employing SOCDTC (3 mol 50 degC 2 h) for Pd-dithiocarbamates catalyst 23

and 26 and SOCDTO (2 mol 50 degC 2 h) for Pd-dithiooxamide catalyst 27 in methanol

solution The solvent was removed under reduced pressure and the products were

purified using a flash column (eluent 32 vv ethyl acetate to n-hexane) to yield of 10-

methoxybenzo[h]quinoline as a pale-yellow solid The result of isolated yield [23 (172

mg 98) 26 (167 mg 95 ) and 27 (163 mg 93)] were comparable with the 1H

NMR integration data [23 26 and 27 (99)]

7482 Reaction B Synthesis of 8-(methoxymethyl)quinoline

In small-scale experiments 8-methylquinoline (425 mg 0297 mmol)

(diacetoxyiodo)benzene ( 1033 mg 0321 mmol) and the selected catalyst (loadings

between 1 - 5 mol) were treated in methanol (25 mL) The reaction mixture was

heated (50 or 100 degC) in a glass vial and stirred using a small magnetic stir bar for a

184

designated time frame [Pd-dithioxamides catalyst (1-5 h) Pd-dithiocarbamates (2-22

h)] The solvent was removed under reduced pressure to yield a yellow crude oil which

was dissolved in deuterated chloroform and analysed by 1H NMR The yield of product

was determined by comparing the integration of methyl resonances (282 ppm) of 8-

methylquinoline with the resonances of methylene (519 ppm) and the methoxy group

(357 ppm) in the 8-(methoxymethyl)quinoline

An isolated yield experiment was carried out on a larger scale of 8-methylquinoline

(120 mg) 2 mol of 25 at 50 degC for 4 h in methanol solution The solvent was removed

by rotary evaporator and the oily product was purified using a flash column (eluent

91 vv hexane to ethyl acetate) to yield 8-(methoxymethyl)quinoline as a yellow oil

The isolated yield obtained (99) was comparable with the 1H NMR spectroscopic

method data (99)

NMR data for the product

10-methoxybenzobenzo[h]quinoline 1H NMR δ = 912 (dd 1H JHH = 40 Hz 20

Hz) 816 (dd 1H J = 80 Hz 20 Hz) 780 (d 1H J = 85 Hz) 767 (d 1H J= 85

Hz) 764 (t 1H J = 80 Hz) 756 (dd 1H J = 80 Hz 10 Hz) 750 (dd 1H J = 80

Hz 20 Hz) 726 (dd 1H J = 80 Hz 10 Hz) 419 (s3H)

10-ethoxybenzobenzo[h]quinoline 1H NMR 1H NMR δ = 911 (dd 1H J = 40 Hz

20 Hz) 816 (dd 1H J = 80 Hz 20 Hz) 778 (d 1H J = 90 Hz) 766 (d 1H J =

90 Hz) 762 (t 1H J = 80 Hz) 756 (dd 1H J = 80 Hz 10 Hz) 750 (dd 1H J =

80 Hz 20 Hz) 728 (dd 1H J = 80 Hz 10 Hz) 445 (q 2H J = 70 Hz) 163 (t

3H J = 70 Hz)

10-isopropoxybenzo[h]quinoline 1H NMR δ = 910 (dd 1H JHH = 45 Hz 20 Hz)

812 (dd 1H J = 80 Hz 20 Hz) 777 (d 1H J = 90 Hz) 763-758 (m 3H) 747

(dd 1H J = 80 Hz 45 Hz) 734 (dd 1H J = 65 Hz 30 Hz) 464 (septet 1H J =

60 Hz) 150 (t 6H J = 60 Hz)

10- trifluoroethoxybenzo[h]quinoline 1H NMR δ = 910 (dd 1H J = 45 Hz 20

Hz) 817 (dd 1H J = 80 Hz 20 Hz) 780 (d 1H J = 85 Hz) 776 (dd 1H J = 75

185

Hz 10 Hz) 770 (d 1H J = 90 Hz) 765 (t 1H J = 80 Hz) 754 (dd 1H J = 80

Hz 45 Hz) 750 (d 1H J = 80 Hz) 474 (septet 2H J = 90 Hz)

8-(methoxymethyl)quinoline 1H NMR δ = 894 (dd 1H J = 42 Hz 14 Hz) 816

(dd 1H J = 82 Hz 18 Hz) 784 (dd 1H J = 70 Hz 10 Hz) 776 (d 1H J = 80

Hz) 756 (t 1H J = 78 Hz) 742 (dd 1H J = 82 Hz 42 Hz) 523 (s2H) 363 (s

3H)

186


751 (TBA)2[Pd2I6]30 (30)

Palladium metal powder (2074 mg 020 mmol) was added to the acetone solution (30

mL) of TBAI (7120 mg 020 mmol) and I2 (5086 mg 020 mmol) and the reaction

mixture was stirred in room temperature Initial brown solution slowly turns into a dark

as reaction proceeds in conjunction with the precipitation of an abundant black

crystalline product The remaining product was obtained by Et2O diffusion into the

reaction solution Yield 1255 mg (86) IR 2960 2860 1460 1370 1170 1110

1070 1030 880 790 740 cmminus1 MS (ES -ve) mz (abundance ) 487(100) [M3]- UVminusvis

342(31760) 456(5900) 549(3800) [λ nm (ε dm3 molminus1 cmminus1)] All the spectroscopic

data agree well with the literature30

752 Trans-PdI2(PPh3)2 (31)

Pd-complex (30) (200 mg 00137 mmol) was dissolved in acetone (5 mL) and stirred

at room temperature for 10 min An acetone solution (5mL) of triphenylphosphine was

added dropwise to the black reaction mixture The reaction mixture slowly turned into

an orange-brown solution was stirred for another 2 h The desire orange precipitate

was filtered washed with ethanol (5 mL) and diethyl ether (5 mL) The product was

then dried under vacuum (219 mg 90) IR (cm-1) 3066 1480 1433 1093 998

745 689 1H NMR δ 773-766 741-735 (m x 2 30H) 31P1H NMR δ 128 (s

PPh3) MS (ES +ve) mz (abundance) 757 (100) [M-I]+

Employing the same procedure as used for the synthesis of 31 PdI2(Me2dazdt)] (28)

(60 mg 010 mmol) triphenylphosphine (517 mg 020 mmol) yielded an orange

precipitate Slow diffusion of diethyl ether into a chloroform solution of the product was

provided deep red crystal of the product The crystal was filtered washed and dried

Yield 827 mg (95) IR 3067 2973 1476 1431 1092 997 746 689 cm-1 1H NMR

δ = 764 ndash 775 (m 30H PPh3) ppm 31P1H NMR δ = 128 (s PPh3) ppm MS (ES

+ve) mz (abundance) 757 (100) [M-I]+

187

753 [PdI2(dppe)] (32)

Employing the same protocols as used for the synthesis of 31 (TBA)2[Pd2I6] (730 mg

005 mmol) and 12-bis(diphenylphosphino)ethane (274 mg 005 mmol) to provide

an orange precipitate Yield 300 mg (79) Similarly PdI2(Me2dazdt)] (28) (30 mg

0048 mmol) triphenylphosphine (197 mg 020 mmol) yielded an orange precipitate

Yield 325 mg (87) IR 3052 1437 1100 998 877 811 701 688 678 cm-1 1H

NMR δ = 233 (d 4H P(CH2)2 JHH = 235 Hz) 743 ndash 796 (m 20H PPh3) ppm 31P

1H NMR δ = 618 (s dppe) ppm All the spectroscopic data reported was well agree

with the literature31

754 [PdI2(dppf)] (33)


005 mmol) and 11-Bis(diphenylphosphino)ferrocene (277 mg 005 mmol) to provide

an orange precipitate (320 mg 70) IR 1714 1480 1359 1302 1219 1167 1092

1101 1040 999 819 745 698 cm-1 1H NMR δ = 417 (br 4H C5H4) 437 (br 4H

C5H4) 739 ndash 751 (m 12H P-Ph) 787 ndash 792 (m 8H P-Ph) ppm 31P 1H NMR δ

= 242 (s dppf) ppm

755 General set up for catalysis reaction

The same procedure for general set up for catalysis reaction used in the previous

section (Chapter 3) was applied in this chapter for the alkoxylation of benzo[h]quinoline

(Reaction A) and methoxy- and acetoxylation of 8-methylquinoline (Reactions B and

C) The detail experimental of Suzuki cross-coupling reaction of selected aryl halides

with phenylboronic acid will be discussed in detailed in Section 7554

188


For small-scale reactions benzo[h]quinoline (500 mg 028 mmol)

(diacetoxyiodo)benzene (1804 mg 056 mmol) and (TBA)2[Pd2I6] (loadings between

1 ndash 2 mol) were treated in the alcohol (25 mL) and heated (50 or 100 degC) for the

designated time (2 4 6 and 24 h) The solvent was removed under reduced pressure

and the resultant crude was analysed by 1H NMR

For the isolated yield reaction benzo[h]quinoline (1500 mg 084 mmol)

(diacetoxyiodo)benzene (5412 mg 168 mmol) and (TBA)2[Pd2I6] (2 mol) were

treated in methanol (75 mL) and heated at 50 degC for 2 h A flash column was used to

purify the product and yield (1699 mg 97) which is slightly lower compared to the

1H NMR integration method (98) This might caused by the human error in purifying

step

For reactions under Sanfordrsquos conditions benzo[h]quinoline (500 mg 028 mmol)

(diacetoxyiodo)benzene (1804 mg 056 mmol) and Pd(OAc)2 (11 mol) were

treated in methanol (25 mL) and heated at 100 degC for the designated time (1 2 5

and 22 h) The solvent was removed under reduced pressure and the resultant crude

was analysed by 1H NMR

For control experiment A benzo[h]quinoline (500 mg 028 mmol) and Pd(OAc)2 (11

mol) were treated in methanol (25 mL) and heated (100 degC) for designated time (1

2 5 and 22 h) The solvent was removed under reduced pressure and the resultant

crude was analysed by 1H NMR

For control experiment B (diacetoxyiodo)benzene (1804 mg 056 mmol) and

Pd(OAc)2 (11 mol) were treated in methanol (25 mL) and heated (100 degC) for

189



For control experiment C Pd(OAc)2 (11 mol) were treated in methanol (25 mL) and

heated (100 degC) for a designated time (1 2 5 and 22 h) The solvent was removed

under reduced pressure and the resultant crude was analysed by 1H NMR

For the independent experiment Pd(OAc)2 (11 mol) were were treated in methanol

(25 mL) and heated at 100 degC for 2 h Then benzo[h]quinoline (500 mg 028 mmol)

and (diacetoxyiodo)benzene (1804 mg 056 mmol) was added and the reaction

mixture was stirred for another 125 and 22 h The solvent was removed under

reduced pressure and the resultant crude was analysed by 1H NMR analyses


For small-scale reaction 8-(methoxymethyl)quinoline (425 mg 0297 mmol)

(diacetoxyiodo)benzene (1033 mg 0321 mmol) and (TBA)2[Pd2I6] (loadings

between 1 ndash 2 mol) were treated in methanol (25 mL) and heated (50 or 100 degC) for

the designated time (2 4 6 and 24 h) The solvent was removed under reduced

pressure and the resultant crude was analysed by 1H NMR

For isolated yield reaction 8-methylquinoline (1275 mg 089 mmol)


treated in methanol (75 mL) heated at 50 degC for 2 h Flash column was used to purify

the product and yield (1452 mg 94) which is slightly lower compared to the 1H NMR

integration method (96)

190

7553 Reaction C Synthesis of 8-(acetoxymethyl)quinoline

8-methylquinoline (425 mg 0297 mmol) (diacetoxyiodo)benzene (1033 mg 0321

mmol) and (TBA)2[Pd2I6] (loadings between 1 ndash 2 mol) were treated in methanol

(25 mL) and heated (50 or 100 degC) for the designated time (2 4 6 and 24 h) The

solvent was removed under reduced pressure and the resultant crude was analysed

by 1H NMR


8-(acetoxymethyl)quinoline 1H NMR δ = 894 (dd 1H JHH = 42 Hz 20 Hz) 815

(dd 1H JHH = 84 Hz 20 Hz) 776 (m 2H) 758 (dd 1H JHH = 82 Hz 74 Hz)

746 (dd 1H JHH = 786 Hz 42 Hz) 586 (s2H) 216 (s 3H)

7554 Reaction D General procedure for Suzuki cross-coupling reactions

Following the literature procedure32 with slight modification aryl halides (05 mmol)

were treated with K2CO3 (15 mmol) in ethanolic solution To this mixture the Pd-

catalyst and the phenylating reagent were added and the reaction mixture was heated

(75 degC) and stirred for a designated time (30 60 90 120 and 150 min) The reaction

progress was monitored by 1H NMR Subsequently the corresponding biphenyl

product was separated by filtration and the reaction mixture was extracted with water

and diethyl ether The organic layer was dried over magnesium sulphate and then

evaporated under reduced pressure to yield a white product The product was purified

by column chromatography using ethyl acetate-n-hexane (140) to yield a comparable

isolated yield

191

In this contribution different types of aryl halides were used such as 4-bromoanisole

4-bromotoluene 4-bromonitrobenzene and 4-iodoanisole The biphenyl product yields

were determined by employing a 1H NMR integration method For the reactions of 4-

bromoanisole and 4-iodoanisole the integrations of their methyl resonances (378

ppm for both) were compared to those of the diagnostic resonance of the methoxy

moiety (386 ppm)33 in the 4-methoxybiphenyl product The yield of 4-methylbiphenyl

was determined by comparing the integration of the methyl resonances of 4-

bromotoulene (230 ppm) with the resonances of the methyl group (238 ppm)34 in the

product Finally the comparison of phenyl resonances of 1-bromo-4-nitrobenzene

(813 ppm) and 4-nitrobiphenyl (828 ppm)35 determined the yields of the last reaction

Three replicate experiments were conducted to collect an average reading


4-methoxybiphenyl 1H NMR δ = 759-754 (m 4H Ar-H) 746-741 (m 4H Ar-H)

735-730 (m1H Ar-H) 702-698 (m 2H Ar-H) 386 (s 3H -OCH3)

4-methylbiphenyl 1H NMR δ = 756 (d 2H J = 72 Hz) 748 (d 2H J = 82 Hz)

741 (t 2H J = 74 Hz) 733 (t 2H J = 76 Hz) 726 (d 2H J = 82 Hz) 238 (s 3H)

4-nitrobiphenyl 1H NMR δ = 828 (d 2H J = 89 Hz) 812-809 (m 2H Ar-H) 769-

766 (m 2H Ar-H) 758-755 (m 2H Ar-H) 741-739 (m 1H Ar-H)

192


761 (MeO)3SiCH2CH2CH2(Me)NCS2K (34)

The starting material 3-trimethoxysilylpropyl-methylamine (1000 mg 517

mmol) was dissolved in acetonitrile (20 mL) and stirred with K2CO3 (2875 mg

2068 mmol) for 30 minutes Carbon disulfide (038 mL 620 mmol) was added

to the solution and stirring continued for 2 hours The solution was filtered to

remove excess K2CO3 and the solvent was removed The residue was dissolved

in chloroform (10 mL) and filtered through diatomaceous earth (Celite) The

solvent was removed to give a yellow oily product Diethyl ether (20 mL) was

added and triturated in an ultrasound bath to give a pale yellow solid product

The solid product separated by filtration washed with diethyl ether (5 mL) and

dried under vacuum Yield 815 mg (52) IR (ATR) 2936 2839 1461 (νCN)

1267 (νC=S) 1187 1063 963 (νC-S) 814 783 cm-1 1H NMR (CDCl3 400 MHz)

δ 064 (t 2H CH2 JHH = 80 Hz) 177 (pent 2H CH2 JHH = 80 Hz) 347 (s

3H NCH3) 355 (s 9H OCH3) 402 (m 2H CH2) ppm 13C1H NMR (CDCl3

101 MHz) δ 58 (s CH2) 199 (s CH2) 426 (s NCH3) 505 (s OCH3) 585 (s

CH2) 2108 (s CS2) ppm MS (ES +ve) mz (abundance) 268 (100) [M]+ Elem

Anal Calcd for C8H18KNO3S2Si (MW = 30755) C 312 H 59 N 46 Found

C 310 H 60 N 45

762 (MeO)3SiCH2CH2CH22NCS2K (35)

Bis(trimethoxysilylpropyl)-amine (1000 mg 293 mmol) was dissolved in

acetonitrile (20 mL) and stirred with potassium carbonate (1620 mg 1172

mmol) for 30 minutes Carbon disulfide (022 mL 352 mmol) was added to the

solution and stirring continued for 2 hours The solution was filtered to remove

excess K2CO3 and the solvent was removed The residue was dissolved in

CHCl3 (10 mL) and filtered through diatomaceous earth (Celite) The solvent

was removed to give a yellow oily product Et2O (20 mL) was added and

triturated in an ultrasound bath to give a pale yellow solid product The solid

product separated by filtration washed with Et2O (5 mL) and dried under

vacuum Yield 773 mg (58) IR (ATR) 2939 2839 1467 (νCN) 1250 (νC=S)

193

1191 1063 965 (νC-S) 783 cm-1 1H NMR (CDCl3 400 MHz) δ 064 (t 4H CH2

JHH = 81 Hz) 183 (m 4H CH2) 358 (s 18H OCH3) 396 (t 4H CH2 JHH =

81 Hz) ppm 13C1H NMR (CDCl3 101 MHz) δ 60 (s CH2) 200 (s CH2) 505

(s OCH3) 562 (s CH2) 2109 (s CS2) ppm MS (ES +ve) mz (abundance)

416 (70) [M]+ Elem Anal Calcd for C13H30KNO6S2Si2 (Mw = 45578) C 343

H 66 N 31 Found C 341 H 67 N 32

763 [(MeO)3SiCH2CH2CH2(Me)NCS2Pd(PPh3)2]PF6 (36)

Compound 34 (258 mg 081 mmol) was dissolved in methanol (10 mL) A chloroform

solution (10 ml) of cis-[PdCl2(PPh3)2] (500 mg 071 mmol) was added followed by

methanolic solution (5 mL) of NH4PF6 (232 mg 142 mmol) The reaction mixture was

refluxed and stirred for 6 h and then all the solvent was removed The residue was

dissolved in minimum amount of chloroform and filtered through Celite All the solvent

removed by reduced pressure Diethyl ether (20 mL) was added and the insoluble

product triturated in a sonic water bath The pale-yellow solid was filtered and washed

with diethyl ether (10 mL) Yield 627 mg (84) IR (ATR) 2941 2840 1480 (νCN)

1261 (νC=S) 1190 1077 963 (νC-S) 831 (νPF) 744 691 cm-1 1H NMR (CDCl3 400

MHz) δ 059 (t 2H CH2 JHH = 82 Hz) 171 (m 2H CH2) 321 (s 3H N-CH3) 355

(s 9H OCH3) 363 (t 2H CH2 JHH = 76 Hz) 732 - 747 (m 30H PPh3) ppm 13C1H

NMR (CDCl3 101 MHz) δ = 61 (s CH2) 203 (s CH2) 366 (s N-CH3) 507 (s

OCH3) 535 (s CH2) 1289 (m om-PC6H5) 1318 (s p-PC6H5) 1340 (ipso-PC6H5

obscured) 1341 (m om-PC6H5) 2065 (s CS2) ppm 31P1H NMR (CDCl3 162

MHz) δ -1465 (sept PF6- JPC = 7124 Hz) 303 306 (d x 2 PPh3 JPP = 350 Hz)

ppm MS (ES +ve) mz (abundance) 898 (100) [M]+ Elem Anal Calcd for

C44H48F6NO3P3PdS2Si (MW = 104442) C 494 H 51 N 12 Found C 498 H

47 N 14

764 [(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37)


solution (10ml) of cis-[PdCl2(PPh3)2] (500 mg 071 mmol) was added followed by a

methanolic solution (5 mL) of NH4PF6 (232 mg 142 mmol) The reaction was refluxed

and stirred for 6 h and then all the solvent removed The residue was dissolved in

194

minimum amount of chloroform and filtered through Celite All the solvent removed by

reduce pressure Diethyl ether (20 mL) was added and the insoluble product triturated

in a sonic bath The pale-yellow solid was filtered and washed with diethyl ether (10

mL) Yield 700 mg (82) IR (ATR) 2941 2840 1480 (νCN) 1267 (νC=S) 1188 1080

965 (νC-S) 835 (νPF) 744 692 cm-1 1H NMR (CDCl3 400 MHz) δ 053 (t 4H CH2

JHH = 83 Hz) 168 (m 4H CH2 JHH = 83 Hz) 352 (s 18H OCH3) 355 (t 4H CH2

JHH = 83 Hz) 728 - 746 (m 30H PPh3) ppm 13C1H NMR (CDCl3 101 MHz) δ 63

(s CH2) 207 (s CH2) 507 (s OCH3) 518 (s CH2) 1289 (tv om-PC6H5 JPC = 53

Hz) 1318 (s p-PC6H5) 1341 (ipso-PC6H5 obscured) 1342 (tv om-PC6H5 JPC =

58 Hz) 2031 (s CS2) ppm 31P1H NMR (CDCl3 162 MHz) δ -1443 (sept PF6-

JPC = 7128 Hz) 305 (s PPh3) ppm MS (ES +ve) mz (abundance) 1047 (88) [M]+

Elem Anal Calcd for C49H60F6NO6P3PdS2Si2middot025CHCl3 (MW = 119264 MW =

122248 as solvate) C 484 H 50 N 12 Found C 484 H 55 N 16

765 Synthesis of silica nanoparticles (SiO2)36 Tetraethyl orthosilicate (5 mL 235 mmol) was dissolved in ethanol (40 mL) Water

(20 mL) was added followed by an ammonia solution (1 mL 165 mmol) The mixture

was stirred for 3 h and a white precipitate was produced The precipitate was collected

by centrifugation (2500 rpm 30 minutes) The liquid was decanted and the white

precipitate was washed with ethanol (3 x 10 mL) The solid product was then dried

under vacuum (038 g)

IR (ATR) 1056 (νasymSiO) 952 (νasymSiOH) 799 (νsymSiO) 528 cm-1


Fresh deoxygenated water was prepared by bubbling nitrogen gas into ultrapure water

for 30 min FeCl3 (162 g 10 mmol) was dissolved in deoxygenated water (10 mL) to

give an orange solution Meanwhile FeCl2 (063 g 5 mmol) was dissolved in freshly

prepared HCl (25 mL 5 mmol) in H2O to give a yellow solution Both solutions were

mixed added to a 07 M ammonium hydroxide solution (125 mL 875 mmol) the

mixture was then stirred vigorously for 30 min under nitrogen The resulting black

precipitate was then separated magnetically and the solvent was discarded Oleic acid

195

(16 mL 5 mmol) was dissolved in acetone (5 mL) and added dropwise to the reaction

mixture and heated at 80 degC for 30 min The resulting precipitate was separated

magnetically washed with acetone (50mL) and re-dissolved in 50 mL of toluene The

resulting solution was centrifuged at 4000 rpm for 1 h to separate any precipitate and

the supernatant liquid was collected and evaporated to dryness to give a brown solid

(129 g)

IR (ATR) 2919 (νasymCH2) 2850 (νsymCH2) 1695 (νsymCO) 1568 (νasymCO) 1404

1089 (νasymCO) 598 (νFeO) cm-1

767 Synthesis of silica-coated iron oxide nanoparticles (SiO2Fe3O4 NP)39

Triton-X45 (112 g 107 mL 0025 mol) was dispersed in cyclohexane (175 mL)

Fe3O4 (50 mg 0213 mmol) was dispersed in cyclohexane (10 mL) and stirred for 30

min until transparent and added into the suspension Ammonia solution (24 mL 28

0035 mol) was then added to form a reverse microemulsion Tetraethylorthosilicate

(193 mL 863 mmol) was introduced and the mixture was stirred for 16 h at room

temperature MeOH (30 mL) was added to form a solid The precipitate was retained

with a magnet while the liquid phase was decanted More MeOH was added and the

mixture was centrifuged (2800 rpm) for 30 min The precipitate was separated and

washed with ethanol (x5) The brown powder was collected and dried (246 g)

IR (ATR) 2287 2000 1634 1451 1055 (νasymSiO) 952 (νasymSiOH) 796 (νsymSiO)

603 563 (νFeO) cm-1

768 Immobilization of complexes 36 and 37 on the SiO2 nanoparticles

The immobilisation of complexes 36 and 37 on the silica nanoparticles was conducted

using a literature protocol with slight modifications40 Under inert conditions (N2) silica

nanoparticles (100 mg) 36 (100 mg 01 mmol) or 37 (100 mg 008 mmol) were

suspended in toluene or chloroform (8 mL) The mixture was refluxed under

continuous stirring overnight The mixture was allowed to cool to room temperature

and was separated by centrifugation (2500 rpm 30 min) The yellow precipitate was

washed with chloroform (5 x 5mL) and the products were dried under vacuum

196

SiO236 NP

IR (ATR) 3207 2000 1440 1055 (νasymSiO) 950(νasymSiOH) 796 (νsymSiO) 692 582

(νFeO) cm-1 TEM measurements were taken of the supported catalyst

SiO236 NP


691 604 (νFeO) cm-1 TEM measurements were taken of the supported catalyst

769 Immobilization of complexes 36 and 37 on the SiO2Fe3O4 nanoparticle

Similarly to immobilisation of complexes 36 and 37 on the silica nanoparticles under

inert condition (N2) silica coated iron-oxide nanoparticle (100 mg) 36 (100 mg 01

mmol) or 37 (100 mg 008 mmol) were suspended in toluene or chloroform (8 mL)

The mixture was refluxed with continuous stirring overnight The mixture was allowed

to cool to room temperature and was separated by centrifugation (2500 rpm 30 min)

The yellow precipitate was washed with chloroform (5 x 5mL) and the products were

dried under vacuum overnight

36SiO2Fe3O4

IR (ATR) 3207 2000 1440 1055 (νasymSiO) 949 (νasymSiOH) 800 (νsymSiO) 692

588 (νFeO) cm-1

TEM and ICP-OES measurements were taken of the supported catalyst

37SiO2Fe3O4

IR (ATR) 3208 1063 (νasymSiO) 944(νasymSiOH) 801(νsymSiO) 692 568 (νFeO) cm-1


197


Employing the same procedure for general set up for catalysis in Chapter 3


For small-scale reaction benzo[h]quinoline (500 mg 028 mmol)

(diacetoxyiodo)benzene (1804 mg 056 mmol) and complex 36 or 37 (loadings

between 1 ndash 2 mol) were treated in the alcohol (25 mL) and heated (50 or 100 degC)

for the designated time (2 4 6 and 24 h) The solvent was removed under reduced


76102 Methoxylation of benzo[h]quinoline using the immobilised Pd-

catalyst system

Benzo[h]quinoline (20 mg 013 mmol) and (diacetoxyiodo)benzene (72 mg 026

mmol) and 36SiO2Fe3O4 or 37SiO2Fe3O4 (3 mol) were treated in the

methanol (25 mL) and heated (50 degC) for the designated time (2 or 22 h) The solvent

was removed under reduced pressure and the resultant crude was analysed by 1H

NMR

The mass of catalyst used in each experiment can be found in the appendix All yields

are calculated with NMR spectroscopic yields (See results and discussion)

198

References





5 J Maurer M Linseis B Sarkar B Schwederski M Niemeyer W Kaim S Zališ C Anson M Zabel and R F Winter J Am Chem Soc 2008 130 259ndash268


7 R Packheiser P Ecorchard T Ruumlffer B Walfort and H Lang Eur J Inorg Chem 2008 4152ndash4165




11 H Schmidbaur A Wohlleben F Wagner O Orama and G Huttner Chem Ber 1977 110 1748ndash1754

12 E Matern J Pikies and G Fritz Zeitschrift fuumlr Anorg und Allg Chemie 2000 626 2136ndash2142








199


21 R Isaksson T Liljefors and J Sandstrom J Chem Res 1981 2 43ndash44




25 R Colton M F Mackay and V Tedesco Inorganica Chim Acta 1993 207 227ndash232













38 P AP V MP and C Pathmamanoharan Langmuir 1994 10 92ndash99


40 J-M Collinson J D E T Wilton-Ely and S Diacuteez-Gonzaacutelez Chem Commun

200

2013 49 11358ndash60

201

Appendices

Appendix A Crystal structure data

A1 Crystal data and structure refinement for [Ru(CH=CHC6H4Me-4)(S2C-

N(CH2py)2)(CO)(PPh3)2] (5)

Table A1 Crystal data and structure refinement for JWE1610

Identification code JWE1610

Formula C59 H51 N3 O P2 Ru S2 C H2 Cl2

Formula weight 113008

Temperature 173(2) K

Diffractometer wavelength Agilent Xcalibur PX Ultra A 154184 Aring

Crystal system space group Triclinic P-1

Unit cell dimensions a = 103952(4) Aring = 76667(4)deg

b = 148523(7) Aring = 82606(3)deg

c = 179728(7) Aring = 87478(3)deg

Volume Z 26773(2) Aring3 2

Density (calculated) 1402 Mgm3

Absorption coefficient 4925 mm-1

202

F(000) 1164

Crystal colour morphology Colourless platy needles

Crystal size 037 x 006 x 002 mm3

range for data collection 3507 to 73825deg

Index ranges -8lt=hlt=12 -18lt=klt=15 -22lt=llt=19

Reflns collected unique 15675 10242 [R(int) = 00428]

Reflns observed [Fgt4(F)] 8362

Absorption correction Analytical

Max and min transmission 0926 and 0509

Refinement method Full-matrix least-squares on F2

Data restraints parameters 10242 0 616

Goodness-of-fit on F2 1075

Final R indices [Fgt4(F)] R1 = 00376 wR2 = 00983

R indices (all data) R1 = 00521 wR2 = 01038

Largest diff peak hole 0578 -0588 eAring-3

Mean and maximum shifterror 0000 and 0001

Table A1 Bond lengths [Aring] and angles [deg] for JWE1610

Ru(1)-C(28) 1836(3)

Ru(1)-C(19) 2083(3)

Ru(1)-P(2) 23706(8)

Ru(1)-P(1) 23823(8)

Ru(1)-S(3) 24740(8)

Ru(1)-S(1) 25025(8)

P(1)-C(29) 1834(3)

P(1)-C(35) 1834(3)

P(1)-C(41) 1845(4)

P(2)-C(53) 1827(3)

P(2)-C(59) 1837(3)

P(2)-C(47) 1845(3)

S(1)-C(2) 1715(3)

C(2)-N(4) 1333(4)

C(2)-S(3) 1698(3)

N(4)-C(5) 1457(5)

N(4)-C(12) 1461(4)

C(5)-C(6) 1516(5)

C(6)-N(7) 1344(5)

C(6)-C(11) 1372(5)

N(7)-C(8) 1353(6)

C(8)-C(9) 1382(7)

C(9)-C(10) 1366(7)

C(10)-C(11) 1368(6)

C(12)-C(13) 1519(6)

C(13)-N(14) 1335(5)

C(13)-C(18) 1370(6)

N(14)-C(15) 1360(7)

C(15)-C(16) 1339(9)

C(16)-C(17) 1354(8)

C(17)-C(18) 1398(7)

C(29)-P(1)-Ru(1) 11804(10)

C(35)-P(1)-Ru(1) 11715(11)

C(41)-P(1)-Ru(1) 11341(12)

C(53)-P(2)-C(59) 10292(15)

C(53)-P(2)-C(47) 10443(14)

C(59)-P(2)-C(47) 9991(14)

C(53)-P(2)-Ru(1) 11295(10)

C(59)-P(2)-Ru(1) 11877(11)

C(47)-P(2)-Ru(1) 11586(11)

C(2)-S(1)-Ru(1) 8783(12)

N(4)-C(2)-S(3) 1241(3)

N(4)-C(2)-S(1) 1227(3)

S(3)-C(2)-S(1) 11319(18)

C(2)-S(3)-Ru(1) 8915(11)

C(2)-N(4)-C(5) 1221(3)

C(2)-N(4)-C(12) 1210(3)

C(5)-N(4)-C(12) 1168(3)

N(4)-C(5)-C(6) 1153(3)

N(7)-C(6)-C(11) 1231(4)

N(7)-C(6)-C(5) 1139(3)

C(11)-C(6)-C(5) 1230(3)

C(6)-N(7)-C(8) 1168(4)

N(7)-C(8)-C(9) 1230(4)

C(10)-C(9)-C(8) 1182(4)

C(9)-C(10)-C(11) 1201(4)

C(10)-C(11)-C(6) 1187(4)

N(4)-C(12)-C(13) 1144(3)

N(14)-C(13)-C(18) 1227(4)

N(14)-C(13)-C(12) 1133(4)

C(18)-C(13)-C(12) 1240(3)

C(13)-N(14)-C(15) 1159(5)

203

C(19)-C(20) 1333(5)

C(20)-C(21) 1477(5)

C(21)-C(22) 1395(5)

C(21)-C(26) 1403(5)

C(22)-C(23) 1388(5)

C(23)-C(24) 1386(6)

C(24)-C(25) 1384(6)

C(24)-C(27) 1519(6)

C(25)-C(26) 1386(5)

C(28)-O(28) 1138(4)

C(29)-C(34) 1388(5)

C(29)-C(30) 1397(5)

C(30)-C(31) 1383(5)

C(31)-C(32) 1387(6)

C(32)-C(33) 1378(6)

C(33)-C(34) 1396(5)

C(35)-C(36) 1373(6)

C(35)-C(40) 1393(5)

C(36)-C(37) 1382(5)

C(37)-C(38) 1380(6)

C(38)-C(39) 1359(7)

C(39)-C(40) 1404(5)

C(41)-C(42) 1383(6)

C(41)-C(46) 1393(5)

C(42)-C(43) 1389(7)

C(43)-C(44) 1372(9)

C(44)-C(45) 1371(8)

C(45)-C(46) 1392(6)

C(47)-C(52) 1386(4)

C(47)-C(48) 1393(5)

C(48)-C(49) 1384(5)

C(49)-C(50) 1384(5)

C(50)-C(51) 1381(6)

C(51)-C(52) 1396(5)

C(53)-C(58) 1388(5)

C(53)-C(54) 1393(5)

C(54)-C(55) 1407(5)

C(55)-C(56) 1375(6)

C(56)-C(57) 1384(6)

C(57)-C(58) 1393(5)

C(59)-C(64) 1384(5)

C(59)-C(60) 1395(5)

C(60)-C(61) 1394(5)

C(61)-C(62) 1381(7)

C(62)-C(63) 1378(7)

C(63)-C(64) 1399(5)

C(28)-Ru(1)-C(19) 9900(14)

C(28)-Ru(1)-P(2) 9001(10)

C(19)-Ru(1)-P(2) 8442(9)

C(28)-Ru(1)-P(1) 8661(11)

C(19)-Ru(1)-P(1) 8546(9)

P(2)-Ru(1)-P(1) 16869(3)

C(28)-Ru(1)-S(3) 16962(11)

C(19)-Ru(1)-S(3) 9137(9)

P(2)-Ru(1)-S(3) 9142(3)

P(1)-Ru(1)-S(3) 9385(3)

C(28)-Ru(1)-S(1) 9981(11)

C(19)-Ru(1)-S(1) 16110(9)

P(2)-Ru(1)-S(1) 9381(3)

P(1)-Ru(1)-S(1) 9739(3)

C(16)-C(15)-N(14) 1249(5)

C(15)-C(16)-C(17) 1188(5)

C(16)-C(17)-C(18) 1187(5)

C(13)-C(18)-C(17) 1190(4)

C(20)-C(19)-Ru(1) 1263(2)

C(19)-C(20)-C(21) 1261(3)

C(22)-C(21)-C(26) 1174(3)

C(22)-C(21)-C(20) 1231(3)

C(26)-C(21)-C(20) 1195(3)

C(23)-C(22)-C(21) 1211(3)

C(24)-C(23)-C(22) 1212(4)

C(25)-C(24)-C(23) 1181(4)

C(25)-C(24)-C(27) 1218(4)

C(23)-C(24)-C(27) 1202(4)

C(24)-C(25)-C(26) 1213(3)

C(25)-C(26)-C(21) 1210(3)

O(28)-C(28)-Ru(1) 1776(3)

C(34)-C(29)-C(30) 1192(3)

C(34)-C(29)-P(1) 1224(3)

C(30)-C(29)-P(1) 1183(3)

C(31)-C(30)-C(29) 1202(3)

C(30)-C(31)-C(32) 1204(3)

C(33)-C(32)-C(31) 1196(3)

C(32)-C(33)-C(34) 1204(4)

C(29)-C(34)-C(33) 1201(3)

C(36)-C(35)-C(40) 1179(3)

C(36)-C(35)-P(1) 1208(3)

C(40)-C(35)-P(1) 1214(3)

C(35)-C(36)-C(37) 1214(4)

C(38)-C(37)-C(36) 1208(5)

C(39)-C(38)-C(37) 1187(4)

C(38)-C(39)-C(40) 1210(4)

C(35)-C(40)-C(39) 1202(4)

C(42)-C(41)-C(46) 1184(4)

C(42)-C(41)-P(1) 1223(3)

C(46)-C(41)-P(1) 1193(3)

C(41)-C(42)-C(43) 1208(5)

C(44)-C(43)-C(42) 1201(5)

C(45)-C(44)-C(43) 1201(4)

C(44)-C(45)-C(46) 1201(4)

C(45)-C(46)-C(41) 1205(4)

C(52)-C(47)-C(48) 1186(3)

C(52)-C(47)-P(2) 1223(3)

C(48)-C(47)-P(2) 1189(2)

C(49)-C(48)-C(47) 1207(3)

C(50)-C(49)-C(48) 1203(4)

C(51)-C(50)-C(49) 1196(3)

C(50)-C(51)-C(52) 1200(3)

C(47)-C(52)-C(51) 1207(3)

C(58)-C(53)-C(54) 1197(3)

C(58)-C(53)-P(2) 1197(2)

C(54)-C(53)-P(2) 1199(3)

C(53)-C(54)-C(55) 1196(3)

C(56)-C(55)-C(54) 1201(3)

C(55)-C(56)-C(57) 1204(3)

C(56)-C(57)-C(58) 1200(4)

C(53)-C(58)-C(57) 1203(3)

C(64)-C(59)-C(60) 1194(3)

C(64)-C(59)-P(2) 1210(3)

C(60)-C(59)-P(2) 1196(3)

C(61)-C(60)-C(59) 1201(4)

204

S(3)-Ru(1)-S(1) 6983(3)

C(29)-P(1)-C(35) 10221(15)

C(29)-P(1)-C(41) 10252(17)

C(35)-P(1)-C(41) 10111(16)

C(62)-C(61)-C(60) 1199(4)

C(63)-C(62)-C(61) 1205(4)

C(62)-C(63)-C(64) 1198(4)

C(59)-C(64)-C(63) 1204(4)

A2 Crystal data and structure refinement for [Ru(dppm)22(micro-dcbpy)] (BPh4)2 (12)



Formula C112 H94 N2 O4 P8 Ru2 2(C24 H20 B)

5(C H2 Cl2)



Diffractometer wavelength Agilent Xcalibur 3 E 071073 Aring

Crystal system space group Monoclinic P21c

Unit cell dimensions a = 113803(4) Aring = 90deg

b = 217537(9) Aring = 92572(4)deg

c = 304002(14) Aring = 90deg

205




F(000) 3136

Crystal colour morphology Yellow blocky needles















Table 2 Bond lengths [Aring] and angles [deg] for JWE1603

Ru(1)-O(3) 2161(4)

Ru(1)-O(1) 2232(4)

Ru(1)-P(43) 22640(16)

Ru(1)-P(13) 22916(17)

Ru(1)-P(11) 23361(16)

Ru(1)-P(41) 23570(16)

Ru(1)-C(2) 2531(6)

O(1)-C(2) 1267(7)

C(2)-O(3) 1260(7)

C(2)-C(4) 1489(8)

C(4)-C(9) 1370(9)

C(4)-C(5) 1380(8)

C(5)-C(6) 1387(8)

C(6)-N(7) 1333(8)

C(6)-C(6)1 1475(12)

N(7)-C(8) 1338(9)

C(8)-C(9) 1390(9)

P(11)-C(20) 1806(6)

P(11)-C(14) 1818(6)

P(11)-C(12) 1829(6)

C(12)-P(13) 1854(6)

P(13)-C(26) 1815(6)

P(13)-C(32) 1820(6)

C(14)-C(15) 1371(9)

C(14)-C(19) 1395(8)

C(15)-C(16) 1395(9)

C(16)-C(17) 1373(10)

C(5)-C(6)-C(6)1 1212(7)

C(6)-N(7)-C(8) 1175(6)

N(7)-C(8)-C(9) 1236(6)

C(4)-C(9)-C(8) 1180(6)

C(20)-P(11)-C(14) 1050(3)

C(20)-P(11)-C(12) 1088(3)

C(14)-P(11)-C(12) 1074(3)

C(20)-P(11)-Ru(1) 1157(2)

C(14)-P(11)-Ru(1) 1235(2)

C(12)-P(11)-Ru(1) 950(2)

P(11)-C(12)-P(13) 948(3)

C(26)-P(13)-C(32) 1043(3)

C(26)-P(13)-C(12) 1024(3)

C(32)-P(13)-C(12) 1072(3)

C(26)-P(13)-Ru(1) 1188(2)

C(32)-P(13)-Ru(1) 1249(2)

C(12)-P(13)-Ru(1) 958(2)

C(15)-C(14)-C(19) 1200(6)

C(15)-C(14)-P(11) 1205(5)

C(19)-C(14)-P(11) 1194(5)

C(14)-C(15)-C(16) 1200(6)

C(17)-C(16)-C(15) 1194(7)

C(18)-C(17)-C(16) 1208(7)

C(17)-C(18)-C(19) 1202(7)

C(18)-C(19)-C(14) 1195(7)

C(25)-C(20)-C(21) 1195(6)

C(25)-C(20)-P(11) 1227(5)

206

C(17)-C(18) 1370(11)

C(18)-C(19) 1377(9)

C(20)-C(25) 1371(9)

C(20)-C(21) 1395(9)

C(21)-C(22) 1370(10)

C(22)-C(23) 1375(12)

C(23)-C(24) 1383(13)

C(24)-C(25) 1397(11)

C(26)-C(31) 1375(9)

C(26)-C(27) 1402(8)

C(27)-C(28) 1383(9)

C(28)-C(29) 1361(10)

C(29)-C(30) 1388(10)

C(30)-C(31) 1384(10)

C(32)-C(37) 1378(9)

C(32)-C(33) 1412(9)

C(33)-C(34) 1376(10)

C(34)-C(35) 1354(11)

C(35)-C(36) 1381(11)

C(36)-C(37) 1385(9)

P(41)-C(50) 1818(6)

P(41)-C(44) 1823(7)

P(41)-C(42) 1851(6)

C(42)-P(43) 1849(6)

P(43)-C(62) 1811(6)

P(43)-C(56) 1829(7)

C(44)-C(49) 1384(9)

C(44)-C(45) 1387(9)

C(45)-C(46) 1383(10)

C(46)-C(47) 1377(12)

C(47)-C(48) 1386(12)

C(48)-C(49) 1366(11)

C(50)-C(55) 1375(9)

C(50)-C(51) 1398(9)

C(51)-C(52) 1386(9)

C(52)-C(53) 1364(11)

C(53)-C(54) 1385(11)

C(54)-C(55) 1382(10)

C(56)-C(57) 1357(9)

C(56)-C(61) 1388(9)

C(57)-C(58) 1392(10)

C(58)-C(59) 1376(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1380(10)

C(62)-C(63) 1386(9)

C(62)-C(67) 1395(8)

C(63)-C(64) 1396(9)

C(64)-C(65) 1362(10)

C(65)-C(66) 1370(10)

C(66)-C(67) 1385(8)

B(70)-C(83) 1628(11)

B(70)-C(77) 1635(11)

B(70)-C(89) 1644(11)

B(70)-C(71) 1659(10)

C(71)-C(76) 1367(10)

C(71)-C(72) 1398(10)

C(72)-C(73) 1367(11)

C(73)-C(74) 1346(13)

C(74)-C(75) 1370(13)

C(75)-C(76) 1403(11)

C(77)-C(82) 1376(10)

C(21)-C(20)-P(11) 1172(5)

C(22)-C(21)-C(20) 1209(7)

C(21)-C(22)-C(23) 1193(8)

C(22)-C(23)-C(24) 1211(8)

C(23)-C(24)-C(25) 1191(8)

C(20)-C(25)-C(24) 1201(7)

C(31)-C(26)-C(27) 1182(6)

C(31)-C(26)-P(13) 1203(5)

C(27)-C(26)-P(13) 1207(5)

C(28)-C(27)-C(26) 1201(6)

C(29)-C(28)-C(27) 1208(6)

C(28)-C(29)-C(30) 1201(7)

C(31)-C(30)-C(29) 1192(7)

C(26)-C(31)-C(30) 1217(7)

C(37)-C(32)-C(33) 1184(6)

C(37)-C(32)-P(13) 1193(5)

C(33)-C(32)-P(13) 1221(5)

C(34)-C(33)-C(32) 1195(7)

C(35)-C(34)-C(33) 1215(7)

C(34)-C(35)-C(36) 1199(7)

C(35)-C(36)-C(37) 1199(8)

C(32)-C(37)-C(36) 1208(7)

C(50)-P(41)-C(44) 1009(3)

C(50)-P(41)-C(42) 1075(3)

C(44)-P(41)-C(42) 1055(3)

C(50)-P(41)-Ru(1) 1224(2)

C(44)-P(41)-Ru(1) 1243(2)

C(42)-P(41)-Ru(1) 9385(19)

P(43)-C(42)-P(41) 952(3)

C(62)-P(43)-C(56) 1029(3)

C(62)-P(43)-C(42) 1067(3)

C(56)-P(43)-C(42) 1063(3)

C(62)-P(43)-Ru(1) 1294(2)

C(56)-P(43)-Ru(1) 1125(2)

C(42)-P(43)-Ru(1) 970(2)

C(49)-C(44)-C(45) 1201(7)

C(49)-C(44)-P(41) 1214(5)

C(45)-C(44)-P(41) 1185(5)

C(46)-C(45)-C(44) 1188(7)

C(47)-C(46)-C(45) 1211(8)

C(46)-C(47)-C(48) 1195(8)

C(49)-C(48)-C(47) 1200(8)

C(48)-C(49)-C(44) 1206(7)

C(55)-C(50)-C(51) 1187(6)

C(55)-C(50)-P(41) 1226(5)

C(51)-C(50)-P(41) 1185(5)

C(52)-C(51)-C(50) 1195(6)

C(53)-C(52)-C(51) 1208(7)

C(52)-C(53)-C(54) 1203(7)

C(55)-C(54)-C(53) 1188(7)

C(50)-C(55)-C(54) 1218(7)

C(57)-C(56)-C(61) 1194(6)

C(57)-C(56)-P(43) 1190(5)

C(61)-C(56)-P(43) 1214(5)

C(56)-C(57)-C(58) 1204(7)

C(59)-C(58)-C(57) 1206(7)

C(60)-C(59)-C(58) 1184(7)

C(59)-C(60)-C(61) 1214(7)

C(60)-C(61)-C(56) 1197(7)

C(63)-C(62)-C(67) 1188(6)

C(63)-C(62)-P(43) 1211(5)

207

C(77)-C(78) 1406(11)

C(78)-C(79) 1390(11)

C(79)-C(80) 1367(12)

C(80)-C(81) 1350(13)

C(81)-C(82) 1412(12)

C(83)-C(88) 1388(11)

C(83)-C(84) 1410(11)

C(84)-C(85) 1398(12)

C(85)-C(86) 1379(14)

C(86)-C(87) 1372(14)

C(87)-C(88) 1399(12)

C(89)-C(94) 1392(10)

C(89)-C(90) 1412(10)

C(90)-C(91) 1387(11)

C(91)-C(92) 1365(13)

C(92)-C(93) 1353(12)

C(93)-C(94) 1402(11)

C(100)-Cl(2) 1707(11)

C(100)-Cl(1) 1727(11)

C(110)-Cl(4) 1639(14)

C(110)-Cl(3) 1720(12)

C(120)-Cl(5) 1670(15)

C(120)-Cl(6) 1751(16)

O(3)-Ru(1)-O(1) 5979(15)

O(3)-Ru(1)-P(43) 9947(12)

O(1)-Ru(1)-P(43) 15664(11)

O(3)-Ru(1)-P(13) 16018(12)

O(1)-Ru(1)-P(13) 10841(11)

P(43)-Ru(1)-P(13) 9445(6)

O(3)-Ru(1)-P(11) 9159(12)

O(1)-Ru(1)-P(11) 9023(11)

P(43)-Ru(1)-P(11) 10176(6)

P(13)-Ru(1)-P(11) 7170(6)

O(3)-Ru(1)-P(41) 9644(12)

O(1)-Ru(1)-P(41) 9776(11)

P(43)-Ru(1)-P(41) 7245(6)

P(13)-Ru(1)-P(41) 10118(6)

P(11)-Ru(1)-P(41) 17076(6)

O(3)-Ru(1)-C(2) 2985(16)

O(1)-Ru(1)-C(2) 3003(16)

P(43)-Ru(1)-C(2) 12894(14)

P(13)-Ru(1)-C(2) 13584(14)

P(11)-Ru(1)-C(2) 8942(13)

P(41)-Ru(1)-C(2) 9982(13)

C(2)-O(1)-Ru(1) 882(3)

O(3)-C(2)-O(1) 1201(5)

O(3)-C(2)-C(4) 1191(5)

O(1)-C(2)-C(4) 1208(5)

O(3)-C(2)-Ru(1) 586(3)

O(1)-C(2)-Ru(1) 618(3)

C(4)-C(2)-Ru(1) 1735(4)

C(2)-O(3)-Ru(1) 916(4)

C(67)-C(62)-P(43) 1201(5)

C(62)-C(63)-C(64) 1199(6)

C(65)-C(64)-C(63) 1203(7)

C(64)-C(65)-C(66) 1207(6)

C(65)-C(66)-C(67) 1197(6)

C(66)-C(67)-C(62) 1206(6)

C(83)-B(70)-C(77) 1137(6)

C(83)-B(70)-C(89) 1124(6)

C(77)-B(70)-C(89) 1039(6)

C(83)-B(70)-C(71) 1032(6)

C(77)-B(70)-C(71) 1114(6)

C(89)-B(70)-C(71) 1124(6)

C(76)-C(71)-C(72) 1146(7)

C(76)-C(71)-B(70) 1245(7)

C(72)-C(71)-B(70) 1209(7)

C(73)-C(72)-C(71) 1239(8)

C(74)-C(73)-C(72) 1201(9)

C(73)-C(74)-C(75) 1188(8)

C(74)-C(75)-C(76) 1206(9)

C(71)-C(76)-C(75) 1219(8)

C(82)-C(77)-C(78) 1150(7)

C(82)-C(77)-B(70) 1238(7)

C(78)-C(77)-B(70) 1208(7)

C(79)-C(78)-C(77) 1230(8)

C(80)-C(79)-C(78) 1199(9)

C(81)-C(80)-C(79) 1191(9)

C(80)-C(81)-C(82) 1211(8)

C(77)-C(82)-C(81) 1220(8)

C(88)-C(83)-C(84) 1154(8)

C(88)-C(83)-B(70) 1249(8)

C(84)-C(83)-B(70) 1196(8)

C(85)-C(84)-C(83) 1222(10)

C(86)-C(85)-C(84) 1197(10)

C(87)-C(86)-C(85) 1201(10)

C(86)-C(87)-C(88) 1194(11)

C(83)-C(88)-C(87) 1232(10)

C(94)-C(89)-C(90) 1145(7)

C(94)-C(89)-B(70) 1249(6)

C(90)-C(89)-B(70) 1204(7)

C(91)-C(90)-C(89) 1227(8)

C(92)-C(91)-C(90) 1202(8)

C(93)-C(92)-C(91) 1196(9)

C(92)-C(93)-C(94) 1206(8)

C(89)-C(94)-C(93) 1224(8)

Cl(2)-C(100)-Cl(1) 1150(7)

Cl(4)-C(110)-Cl(3) 1199(8)

Cl(5)-C(120)-Cl(6) 1119(9)

208

A3 Crystal data and structure refinement for [(Ph3P)Au(SC6H4CO24)Ru CH=CHbpyReCl (CO)3(CO)(PPh3)2] (22)



Formula C77 H58 Au Cl N2 O6 P3 Re Ru S

25(C H2 Cl2)






b = 147789(5) Aring = 73377(3)deg

c = 214417(6) Aring = 75105(3)deg




F(000) 1926

Crystal colour morphology Orange blocks






209











Au(1)-P(11) 22545(16)

Au(1)-S(10) 23027(16)

Re(1)-C(83) 1895(7)

Re(1)-C(84) 1915(7)

Re(1)-C(85) 1931(9)

Re(1)-C(85) 1947(7)

Re(1)-N(43) 2161(5)

Re(1)-N(32) 2175(5)

Re(1)-Cl(1) 2271(8)

Re(1)-Cl(1) 2337(4)

Ru(1)-C(82) 1807(6)

Ru(1)-C(30) 2013(5)

Ru(1)-O(1) 2194(3)

Ru(1)-O(3) 2236(4)

Ru(1)-P(63) 23781(16)

Ru(1)-P(44) 23806(17)

Ru(1)-C(2) 2564(5)

C(85)-O(85) 1187(8)

C(85)-O(85) 1178(9)

O(1)-C(2) 1255(7)

C(2)-O(3) 1268(7)

C(2)-C(4) 1480(7)

C(4)-C(9) 1377(8)

C(4)-C(5) 1399(8)

C(5)-C(6) 1360(8)

C(6)-C(7) 1376(8)

C(7)-C(8) 1376(8)

C(7)-S(10) 1761(6)

C(8)-C(9) 1392(8)

P(11)-C(18) 1800(6)

P(11)-C(24) 1811(6)

P(11)-C(12) 1824(6)

C(12)-C(13) 1386(8)

C(12)-C(17) 1388(9)

C(13)-C(14) 1360(10)

C(14)-C(15) 1383(11)

C(15)-C(16) 1395(10)

C(16)-C(17) 1366(9)

C(18)-C(23) 1374(9)

C(18)-C(19) 1405(9)

C(19)-C(20) 1388(9)

C(20)-C(21) 1378(10)

C(21)-C(22) 1346(11)

C(30)-Ru(1)-C(2) 1308(2)

O(1)-Ru(1)-C(2) 2928(16)

O(3)-Ru(1)-C(2) 2965(16)

P(63)-Ru(1)-C(2) 8971(14)

P(44)-Ru(1)-C(2) 8897(14)

O(85)-C(85)-Re(1) 1747(13)

O(85)-C(85)-Re(1) 176(4)

C(2)-O(1)-Ru(1) 919(3)

O(1)-C(2)-O(3) 1194(5)

O(1)-C(2)-C(4) 1223(5)

O(3)-C(2)-C(4) 1183(5)

O(1)-C(2)-Ru(1) 588(3)

O(3)-C(2)-Ru(1) 607(3)

C(4)-C(2)-Ru(1) 1784(4)

C(2)-O(3)-Ru(1) 897(3)

C(9)-C(4)-C(5) 1186(5)

C(9)-C(4)-C(2) 1207(5)

C(5)-C(4)-C(2) 1207(6)

C(6)-C(5)-C(4) 1199(6)

C(5)-C(6)-C(7) 1226(6)

C(8)-C(7)-C(6) 1176(5)

C(8)-C(7)-S(10) 1237(5)

C(6)-C(7)-S(10) 1187(5)

C(7)-C(8)-C(9) 1212(6)

C(4)-C(9)-C(8) 1202(6)

C(7)-S(10)-Au(1) 1059(2)

C(18)-P(11)-C(24) 1048(3)

C(18)-P(11)-C(12) 1061(3)

C(24)-P(11)-C(12) 1055(3)

C(18)-P(11)-Au(1) 1112(2)

C(24)-P(11)-Au(1) 1164(2)

C(12)-P(11)-Au(1) 1120(2)

C(13)-C(12)-C(17) 1192(6)

C(13)-C(12)-P(11) 1191(5)

C(17)-C(12)-P(11) 1217(5)

C(14)-C(13)-C(12) 1206(7)

C(13)-C(14)-C(15) 1207(7)

C(14)-C(15)-C(16) 1188(6)

C(17)-C(16)-C(15) 1204(7)

C(16)-C(17)-C(12) 1203(7)

C(23)-C(18)-C(19) 1183(6)

C(23)-C(18)-P(11) 1231(5)

C(19)-C(18)-P(11) 1186(5)

210

C(22)-C(23) 1422(10)

C(24)-C(25) 1378(9)

C(24)-C(29) 1384(8)

C(25)-C(26) 1368(9)

C(26)-C(27) 1380(10)

C(27)-C(28) 1370(10)

C(28)-C(29) 1387(9)

C(30)-C(31) 1331(7)

C(31)-C(34) 1456(8)

N(32)-C(33) 1326(7)

N(32)-C(37) 1356(7)

C(33)-C(34) 1390(8)

C(34)-C(35) 1399(8)

C(35)-C(36) 1363(8)

C(36)-C(37) 1384(8)

C(37)-C(38) 1482(8)

C(38)-N(43) 1341(7)

C(38)-C(39) 1372(8)

C(39)-C(40) 1386(9)

C(40)-C(41) 1364(9)

C(41)-C(42) 1371(9)

C(42)-N(43) 1347(8)

P(44)-C(45) 1819(7)

P(44)-C(57) 1820(7)

P(44)-C(51) 1830(4)

P(44)-C(51) 1861(15)

C(45)-C(46) 1379(10)

C(45)-C(50) 1385(10)

C(46)-C(47) 1356(10)

C(47)-C(48) 1331(14)

C(48)-C(49) 1359(13)

C(49)-C(50) 1397(11)

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(57)-C(58) 1390(9)

C(57)-C(62) 1396(9)

C(58)-C(59) 1396(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1366(10)

C(61)-C(62) 1401(9)

P(63)-C(70) 1812(7)

P(63)-C(76) 1817(9)

P(63)-C(76) 1831(5)

P(63)-C(64) 1831(6)

C(64)-C(65) 1367(9)

C(64)-C(69) 1379(8)

C(65)-C(66) 1381(9)

C(66)-C(67) 1352(9)

C(67)-C(68) 1382(10)

C(68)-C(69) 1394(8)

C(70)-C(75) 1371(10)

C(20)-C(19)-C(18) 1209(6)

C(21)-C(20)-C(19) 1208(7)

C(22)-C(21)-C(20) 1184(7)

C(21)-C(22)-C(23) 1227(7)

C(18)-C(23)-C(22) 1189(7)

C(25)-C(24)-C(29) 1188(6)

C(25)-C(24)-P(11) 1219(5)

C(29)-C(24)-P(11) 1190(5)

C(26)-C(25)-C(24) 1212(6)

C(25)-C(26)-C(27) 1195(7)

C(28)-C(27)-C(26) 1206(7)

C(27)-C(28)-C(29) 1194(7)

C(24)-C(29)-C(28) 1205(7)

C(31)-C(30)-Ru(1) 1354(5)

C(30)-C(31)-C(34) 1249(6)

C(33)-N(32)-C(37) 1176(5)

C(33)-N(32)-Re(1) 1254(4)

C(37)-N(32)-Re(1) 1168(4)

N(32)-C(33)-C(34) 1257(6)

C(33)-C(34)-C(35) 1148(5)

C(33)-C(34)-C(31) 1212(5)

C(35)-C(34)-C(31) 1239(5)

C(36)-C(35)-C(34) 1211(6)

C(35)-C(36)-C(37) 1194(6)

N(32)-C(37)-C(36) 1213(5)

N(32)-C(37)-C(38) 1151(5)

C(36)-C(37)-C(38) 1235(5)

N(43)-C(38)-C(39) 1214(6)

N(43)-C(38)-C(37) 1151(5)

C(39)-C(38)-C(37) 1234(6)

C(38)-C(39)-C(40) 1208(6)

C(41)-C(40)-C(39) 1172(6)

C(40)-C(41)-C(42) 1201(6)

N(43)-C(42)-C(41) 1226(6)

C(38)-N(43)-C(42) 1179(5)

C(38)-N(43)-Re(1) 1180(4)

C(42)-N(43)-Re(1) 1241(4)

C(45)-P(44)-C(57) 1029(3)

C(45)-P(44)-C(51) 1036(4)

C(57)-P(44)-C(51) 1002(4)

C(45)-P(44)-C(51) 1043(12)

C(57)-P(44)-C(51) 1099(10)

C(45)-P(44)-Ru(1) 1140(2)

C(57)-P(44)-Ru(1) 1181(2)

C(51)-P(44)-Ru(1) 1160(3)

C(51)-P(44)-Ru(1) 1068(12)

C(46)-C(45)-C(50) 1180(7)

C(46)-C(45)-P(44) 1194(6)

C(50)-C(45)-P(44) 1226(6)

C(47)-C(46)-C(45) 1219(8)

C(48)-C(47)-C(46) 1204(9)

C(47)-C(48)-C(49) 1203(8)

C(48)-C(49)-C(50) 1208(9)

C(45)-C(50)-C(49) 1186(8)

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1173(4)

C(56)-C(51)-P(44) 1227(4)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

211

C(70)-C(71) 1386(9)

C(71)-C(72) 1392(12)

C(72)-C(73) 1341(13)

C(73)-C(74) 1368(13)

C(74)-C(75) 1396(11)

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(82)-O(82) 1152(7)

C(83)-O(83) 1152(7)

C(84)-O(84) 1138(8)

P(11)-Au(1)-S(10) 17634(6)

C(83)-Re(1)-C(84) 865(3)

C(83)-Re(1)-C(85) 861(15)

C(84)-Re(1)-C(85) 924(15)

C(83)-Re(1)-C(85) 896(5)

C(84)-Re(1)-C(85) 887(5)

C(83)-Re(1)-N(43) 1003(2)

C(84)-Re(1)-N(43) 1732(2)

C(85)-Re(1)-N(43) 884(14)

C(85)-Re(1)-N(43) 910(5)

C(83)-Re(1)-N(32) 1743(2)

C(84)-Re(1)-N(32) 986(2)

C(85)-Re(1)-N(32) 913(15)

C(85)-Re(1)-N(32) 930(5)

N(43)-Re(1)-N(32) 7463(18)

C(83)-Re(1)-Cl(1) 974(3)

C(84)-Re(1)-Cl(1) 941(3)

C(85)-Re(1)-Cl(1) 1729(14)

N(43)-Re(1)-Cl(1) 848(2)

N(32)-Re(1)-Cl(1) 847(2)

C(83)-Re(1)-Cl(1) 873(3)

C(84)-Re(1)-Cl(1) 926(3)

C(85)-Re(1)-Cl(1) 1766(5)

N(43)-Re(1)-Cl(1) 8805(17)

N(32)-Re(1)-Cl(1) 8998(17)

C(82)-Ru(1)-C(30) 917(3)

C(82)-Ru(1)-O(1) 1667(2)

C(30)-Ru(1)-O(1) 10156(19)

C(82)-Ru(1)-O(3) 1078(2)

C(30)-Ru(1)-O(3) 1604(2)

O(1)-Ru(1)-O(3) 5893(14)

C(82)-Ru(1)-P(63) 8796(19)

C(30)-Ru(1)-P(63) 9106(17)

O(1)-Ru(1)-P(63) 9197(11)

O(3)-Ru(1)-P(63) 8801(11)

C(82)-Ru(1)-P(44) 9536(19)

C(30)-Ru(1)-P(44) 8717(17)

O(1)-Ru(1)-P(44) 8519(11)

O(3)-Ru(1)-P(44) 9255(11)

P(63)-Ru(1)-P(44) 17628(6)

C(55)-C(56)-C(51) 1200

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1203(18)

C(56)-C(51)-P(44) 1196(18)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

C(55)-C(56)-C(51) 1200

C(58)-C(57)-C(62) 1183(6)

C(58)-C(57)-P(44) 1217(6)

C(62)-C(57)-P(44) 1199(5)

C(57)-C(58)-C(59) 1199(8)

C(60)-C(59)-C(58) 1211(8)

C(61)-C(60)-C(59) 1200(7)

C(60)-C(61)-C(62) 1198(7)

C(57)-C(62)-C(61) 1208(7)

C(70)-P(63)-C(76) 1091(6)

C(70)-P(63)-C(76) 1009(4)

C(70)-P(63)-C(64) 1038(3)

C(76)-P(63)-C(64) 1055(7)

C(76)-P(63)-C(64) 1038(5)

C(70)-P(63)-Ru(1) 1150(2)

C(76)-P(63)-Ru(1) 1081(6)

C(76)-P(63)-Ru(1) 1166(4)

C(64)-P(63)-Ru(1) 11489(19)

C(65)-C(64)-C(69) 1180(6)

C(65)-C(64)-P(63) 1231(4)

C(69)-C(64)-P(63) 1189(5)

C(64)-C(65)-C(66) 1216(6)

C(67)-C(66)-C(65) 1204(7)

C(66)-C(67)-C(68) 1196(6)

C(67)-C(68)-C(69) 1195(6)

C(64)-C(69)-C(68) 1208(7)

C(75)-C(70)-C(71) 1178(7)

C(75)-C(70)-P(63) 1200(5)

C(71)-C(70)-P(63) 1221(6)

C(70)-C(71)-C(72) 1205(8)

C(73)-C(72)-C(71) 1195(8)

C(72)-C(73)-C(74) 1225(9)

C(73)-C(74)-C(75) 1173(10)

C(70)-C(75)-C(74) 1223(8)

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1210(6)

C(81)-C(76)-P(63) 1190(6)

C(76)-C(77)-C(78) 1200

C(79)-C(78)-C(77) 1200

C(78)-C(79)-C(80) 1200

C(81)-C(80)-C(79) 1200

C(80)-C(81)-C(76) 1200

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1215(10)

C(81)-C(76)-P(63) 1184(10)

C(78)-C(77)-C(76) 1200

C(77)-C(78)-C(79) 1200

C(80)-C(79)-C(78) 1200

C(79)-C(80)-C(81) 1200

C(80)-C(81)-C(76) 1200

O(82)-C(82)-Ru(1) 1771(5)

O(83)-C(83)-Re(1) 1771(7)

O(84)-C(84)-Re(1) 1793(6)

212

C(82)-Ru(1)-C(2) 1374(2)

A4 Crystal data and structure refinement for [(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25-A)

Table 1 Crystal data and structure refinement for JWE1608


Formula C78 H68 N2 P4 Pd2 S4 2(F6 P) C4 H10 O




Crystal system space group Monoclinic P21n


b = 155218(4) Aring = 107289(3)deg

c = 268129(9) Aring = 90deg




F(000) 3784

Crystal colour morphology Yellow blocks





213












Pd(1)-P(2) 22948(10)

Pd(1)-P(1) 23232(10)

Pd(1)-S(3) 23304(10)

Pd(1)-S(1) 23536(10)

Pd(2)-P(4) 22985(10)

Pd(2)-S(12) 23240(10)

Pd(2)-P(3) 23292(10)

Pd(2)-S(10) 23512(10)

P(1)-C(13) 1814(4)

P(1)-C(25) 1815(4)

P(1)-C(19) 1818(4)

P(2)-C(31) 1809(4)

P(2)-C(43) 1810(4)

P(2)-C(37) 1823(4)

P(3)-C(49) 1805(4)

P(3)-C(61) 1822(4)

P(3)-C(55) 1822(4)

P(4)-C(79) 1818(4)

P(4)-C(67) 1821(4)

P(4)-C(73) 1826(4)

S(1)-C(2) 1735(4)

C(2)-N(4) 1302(5)

C(2)-S(3) 1722(4)

N(4)-C(5) 1458(5)

N(4)-C(9) 1478(5)

C(5)-C(6) 1524(6)

C(6)-N(7) 1473(5)

N(7)-C(11) 1308(5)

N(7)-C(8) 1464(5)

C(8)-C(9) 1511(6)

S(10)-C(11) 1728(4)

C(11)-S(12) 1717(4)

C(13)-C(18) 1380(6)

C(13)-C(14) 1383(6)

C(14)-C(15) 1384(7)

C(15)-C(16) 1371(8)

C(16)-C(17) 1341(8)

C(17)-C(18) 1383(7)

C(19)-C(24) 1371(6)

C(19)-C(20) 1392(6)

C(20)-C(21) 1372(7)

C(79)-P(4)-C(73) 9763(18)

C(67)-P(4)-C(73) 1063(2)

C(79)-P(4)-Pd(2) 11555(13)

C(67)-P(4)-Pd(2) 10862(13)

C(73)-P(4)-Pd(2) 11746(14)

C(2)-S(1)-Pd(1) 8607(13)

N(4)-C(2)-S(3) 1232(3)

N(4)-C(2)-S(1) 1256(3)

S(3)-C(2)-S(1) 1112(2)

C(2)-S(3)-Pd(1) 8709(14)

C(2)-N(4)-C(5) 1228(3)

C(2)-N(4)-C(9) 1227(3)

C(5)-N(4)-C(9) 1145(3)

N(4)-C(5)-C(6) 1090(3)

N(7)-C(6)-C(5) 1095(3)

C(11)-N(7)-C(8) 1244(3)

C(11)-N(7)-C(6) 1220(3)

C(8)-N(7)-C(6) 1133(3)

N(7)-C(8)-C(9) 1103(3)

N(4)-C(9)-C(8) 1100(3)

C(11)-S(10)-Pd(2) 8619(13)

N(7)-C(11)-S(12) 1234(3)

N(7)-C(11)-S(10) 1253(3)

S(12)-C(11)-S(10) 1112(2)

C(11)-S(12)-Pd(2) 8729(13)

C(18)-C(13)-C(14) 1183(4)

C(18)-C(13)-P(1) 1234(3)

C(14)-C(13)-P(1) 1183(3)

C(13)-C(14)-C(15) 1211(5)

C(16)-C(15)-C(14) 1195(5)

C(17)-C(16)-C(15) 1194(5)

C(16)-C(17)-C(18) 1223(5)

C(13)-C(18)-C(17) 1192(5)

C(24)-C(19)-C(20) 1199(4)

C(24)-C(19)-P(1) 1194(3)

C(20)-C(19)-P(1) 1207(4)

C(21)-C(20)-C(19) 1199(5)

C(22)-C(21)-C(20) 1206(6)

C(21)-C(22)-C(23) 1211(5)

C(22)-C(23)-C(24) 1187(6)

214

C(21)-C(22) 1342(9)

C(22)-C(23) 1390(9)

C(23)-C(24) 1402(7)

C(25)-C(30) 1390(5)

C(25)-C(26) 1405(5)

C(26)-C(27) 1377(6)

C(27)-C(28) 1380(6)

C(28)-C(29) 1375(6)

C(29)-C(30) 1380(6)

C(31)-C(32) 1390(6)

C(31)-C(36) 1392(6)

C(32)-C(33) 1387(6)

C(33)-C(34) 1380(8)

C(34)-C(35) 1365(8)

C(35)-C(36) 1384(7)

C(37)-C(42) 1379(6)

C(37)-C(38) 1388(6)

C(38)-C(39) 1382(6)

C(39)-C(40) 1367(7)

C(40)-C(41) 1356(7)

C(41)-C(42) 1386(6)

C(43)-C(44) 1381(6)

C(43)-C(48) 1393(6)

C(44)-C(45) 1394(7)

C(45)-C(46) 1373(8)

C(46)-C(47) 1365(8)

C(47)-C(48) 1390(6)

C(49)-C(50) 1388(5)

C(49)-C(54) 1402(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1360(6)

C(52)-C(53) 1384(6)

C(53)-C(54) 1372(6)

C(55)-C(56) 1390(5)

C(55)-C(60) 1393(5)

C(56)-C(57) 1385(6)

C(57)-C(58) 1374(6)

C(58)-C(59) 1375(6)

C(59)-C(60) 1377(6)

C(61)-C(66) 1393(6)

C(61)-C(62) 1394(6)

C(62)-C(63) 1388(6)

C(63)-C(64) 1379(7)

C(64)-C(65) 1373(7)

C(65)-C(66) 1384(6)

C(67)-C(72) 1387(6)

C(67)-C(68) 1387(6)

C(68)-C(69) 1378(6)

C(69)-C(70) 1362(7)

C(70)-C(71) 1375(8)

C(71)-C(72) 1376(7)

C(73)-C(78) 1371(6)

C(73)-C(74) 1392(6)

C(74)-C(75) 1371(7)

C(75)-C(76) 1369(8)

C(76)-C(77) 1376(8)

C(77)-C(78) 1410(6)

C(79)-C(84) 1384(5)

C(79)-C(80) 1394(5)

C(80)-C(81) 1374(6)

C(81)-C(82) 1387(6)

C(19)-C(24)-C(23) 1198(5)

C(30)-C(25)-C(26) 1184(4)

C(30)-C(25)-P(1) 1208(3)

C(26)-C(25)-P(1) 1207(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1200(4)

C(29)-C(28)-C(27) 1201(4)

C(28)-C(29)-C(30) 1205(4)

C(29)-C(30)-C(25) 1204(4)

C(32)-C(31)-C(36) 1193(4)

C(32)-C(31)-P(2) 1192(3)

C(36)-C(31)-P(2) 1214(4)

C(33)-C(32)-C(31) 1204(5)

C(34)-C(33)-C(32) 1195(5)

C(35)-C(34)-C(33) 1205(5)

C(34)-C(35)-C(36) 1207(5)

C(35)-C(36)-C(31) 1196(5)

C(42)-C(37)-C(38) 1188(4)

C(42)-C(37)-P(2) 1230(3)

C(38)-C(37)-P(2) 1180(3)

C(39)-C(38)-C(37) 1200(4)

C(40)-C(39)-C(38) 1204(5)

C(41)-C(40)-C(39) 1201(4)

C(40)-C(41)-C(42) 1204(5)

C(37)-C(42)-C(41) 1203(4)

C(44)-C(43)-C(48) 1202(4)

C(44)-C(43)-P(2) 1243(4)

C(48)-C(43)-P(2) 1154(3)

C(43)-C(44)-C(45) 1192(5)

C(46)-C(45)-C(44) 1201(5)

C(47)-C(46)-C(45) 1211(5)

C(46)-C(47)-C(48) 1196(5)

C(47)-C(48)-C(43) 1198(5)

C(50)-C(49)-C(54) 1191(4)

C(50)-C(49)-P(3) 1196(3)

C(54)-C(49)-P(3) 1212(3)

C(49)-C(50)-C(51) 1197(4)

C(52)-C(51)-C(50) 1202(4)

C(51)-C(52)-C(53) 1209(4)

C(54)-C(53)-C(52) 1197(4)

C(53)-C(54)-C(49) 1204(4)

C(56)-C(55)-C(60) 1185(4)

C(56)-C(55)-P(3) 1219(3)

C(60)-C(55)-P(3) 1193(3)

C(57)-C(56)-C(55) 1200(4)

C(58)-C(57)-C(56) 1208(4)

C(57)-C(58)-C(59) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(59)-C(60)-C(55) 1209(4)

C(66)-C(61)-C(62) 1187(4)

C(66)-C(61)-P(3) 1201(3)

C(62)-C(61)-P(3) 1211(3)

C(63)-C(62)-C(61) 1199(4)

C(64)-C(63)-C(62) 1208(5)

C(65)-C(64)-C(63) 1194(4)

C(64)-C(65)-C(66) 1207(5)

C(65)-C(66)-C(61) 1204(4)

C(72)-C(67)-C(68) 1191(4)

C(72)-C(67)-P(4) 1188(3)

C(68)-C(67)-P(4) 1215(3)

C(69)-C(68)-C(67) 1199(5)

215

C(82)-C(83) 1375(6)

C(83)-C(84) 1368(5)

P(10)-F(13) 1549(4)

P(10)-F(15) 1560(4)

P(10)-F(14) 1560(3)

P(10)-F(12) 1564(4)

P(10)-F(11) 1582(3)

P(10)-F(16) 1592(3)

P(20)-F(23) 1557(3)

P(20)-F(21) 1565(3)

P(20)-F(26) 1573(3)

P(20)-F(24) 1582(3)

P(20)-F(22) 1584(3)

P(20)-F(25) 1589(3)

O(90)-C(91) 1361(6)

O(90)-C(93) 1397(7)

C(91)-C(92) 1483(8)

C(93)-C(94) 1393(8)

O(90)-C(91) 1341(10)

O(90)-C(93) 1345(10)

C(91)-C(92) 1452(10)

C(93)-C(94) 1451(10)

P(2)-Pd(1)-P(1) 10098(4)

P(2)-Pd(1)-S(3) 16943(4)

P(1)-Pd(1)-S(3) 8822(4)

P(2)-Pd(1)-S(1) 9507(4)

P(1)-Pd(1)-S(1) 16140(4)

S(3)-Pd(1)-S(1) 7504(4)

P(4)-Pd(2)-S(12) 17025(4)

P(4)-Pd(2)-P(3) 10004(4)

S(12)-Pd(2)-P(3) 8970(3)

P(4)-Pd(2)-S(10) 9535(3)

S(12)-Pd(2)-S(10) 7490(3)

P(3)-Pd(2)-S(10) 16452(4)

C(13)-P(1)-C(25) 10983(18)

C(13)-P(1)-C(19) 1033(2)

C(25)-P(1)-C(19) 10175(19)

C(13)-P(1)-Pd(1) 10736(14)

C(25)-P(1)-Pd(1) 10878(12)

C(19)-P(1)-Pd(1) 12519(13)

C(31)-P(2)-C(43) 10980(19)

C(31)-P(2)-C(37) 10173(17)

C(43)-P(2)-C(37) 10461(19)

C(31)-P(2)-Pd(1) 11826(15)

C(43)-P(2)-Pd(1) 10682(14)

C(37)-P(2)-Pd(1) 11481(13)

C(49)-P(3)-C(61) 10500(18)

C(49)-P(3)-C(55) 10370(18)

C(61)-P(3)-C(55) 10515(18)

C(49)-P(3)-Pd(2) 11419(12)

C(61)-P(3)-Pd(2) 11999(13)

C(55)-P(3)-Pd(2) 10732(12)

C(79)-P(4)-C(67) 11063(18)

C(70)-C(69)-C(68) 1209(5)

C(69)-C(70)-C(71) 1194(5)

C(70)-C(71)-C(72) 1209(5)

C(71)-C(72)-C(67) 1197(5)

C(78)-C(73)-C(74) 1201(4)

C(78)-C(73)-P(4) 1194(3)

C(74)-C(73)-P(4) 1189(3)

C(75)-C(74)-C(73) 1205(5)

C(76)-C(75)-C(74) 1197(5)

C(75)-C(76)-C(77) 1209(5)

C(76)-C(77)-C(78) 1196(5)

C(73)-C(78)-C(77) 1191(5)

C(84)-C(79)-C(80) 1198(4)

C(84)-C(79)-P(4) 1151(3)

C(80)-C(79)-P(4) 1246(3)

C(81)-C(80)-C(79) 1192(4)

C(80)-C(81)-C(82) 1206(4)

C(83)-C(82)-C(81) 1199(4)

C(84)-C(83)-C(82) 1201(4)

C(83)-C(84)-C(79) 1205(4)

F(13)-P(10)-F(15) 1779(3)

F(13)-P(10)-F(14) 913(3)

F(15)-P(10)-F(14) 902(3)

F(13)-P(10)-F(12) 903(3)

F(15)-P(10)-F(12) 882(3)

F(14)-P(10)-F(12) 1775(3)

F(13)-P(10)-F(11) 914(2)

F(15)-P(10)-F(11) 901(2)

F(14)-P(10)-F(11) 915(2)

F(12)-P(10)-F(11) 903(2)

F(13)-P(10)-F(16) 891(2)

F(15)-P(10)-F(16) 8948(19)

F(14)-P(10)-F(16) 8896(18)

F(12)-P(10)-F(16) 892(2)

F(11)-P(10)-F(16) 1793(2)

F(23)-P(20)-F(21) 896(2)

F(23)-P(20)-F(26) 923(2)

F(21)-P(20)-F(26) 1778(2)

F(23)-P(20)-F(24) 9177(19)

F(21)-P(20)-F(24) 8826(17)

F(26)-P(20)-F(24) 9056(16)

F(23)-P(20)-F(22) 893(2)

F(21)-P(20)-F(22) 9091(19)

F(26)-P(20)-F(22) 9024(18)

F(24)-P(20)-F(22) 1787(2)

F(23)-P(20)-F(25) 1794(2)

F(21)-P(20)-F(25) 908(2)

F(26)-P(20)-F(25) 873(2)

F(24)-P(20)-F(25) 8868(19)

F(22)-P(20)-F(25) 903(2)

C(91)-O(90)-C(93) 1125(6)

O(90)-C(91)-C(92) 1100(6)

C(94)-C(93)-O(90) 1137(7)

C(91)-O(90)-C(93) 119(2)

O(90)-C(91)-C(92) 1157(17)

O(90)-C(93)-C(94) 1167(17)

216

A5 Crystal data and structure refinement for [(Ph3P)2Pd(S2CNC4H8NCS2)Pd(PPh3)2][PF6]2 (25-B)









b = 107032(4) Aring = 78500(4)deg

c = 212565(12) Aring = 88333(3)deg




F(000) 946









217









Pd(1)-P(2) 22888(9)

Pd(1)-P(1) 23146(9)

Pd(1)-S(1) 23388(8)

Pd(1)-S(3) 23479(9)

P(1)-C(7) 1816(4)

P(1)-C(13) 1817(3)

P(1)-C(19) 1825(4)

P(2)-C(25) 1809(4)

P(2)-C(37) 1821(4)

P(2)-C(31) 1822(4)

S(1)-C(2) 1727(4)

C(2)-N(4) 1326(4)

C(2)-S(3) 1714(4)

N(4)-C(5) 1463(5)

N(4)-C(6) 1480(5)

C(5)-C(6)1 1519(6)

C(6)-C(5)1 1519(6)

C(7)-C(8) 1398(6)

C(7)-C(12) 1399(5)

C(8)-C(9) 1378(6)

C(9)-C(10) 1379(7)

C(10)-C(11) 1390(8)

C(11)-C(12) 1369(7)

C(13)-C(14) 1386(6)

C(13)-C(18) 1392(5)

C(14)-C(15) 1389(5)

C(15)-C(16) 1380(6)

C(16)-C(17) 1381(7)

C(17)-C(18) 1397(5)

C(19)-C(24) 1383(6)

C(19)-C(20) 1386(6)

C(20)-C(21) 1388(6)

C(21)-C(22) 1375(8)

C(22)-C(23) 1370(9)

C(23)-C(24) 1407(7)

C(25)-C(30) 1394(6)

C(25)-C(26) 1396(6)

C(26)-C(27) 1379(6)

C(27)-C(28) 1384(8)

C(28)-C(29) 1365(8)

C(29)-C(30) 1395(6)

C(31)-C(32) 1389(5)

C(31)-C(36) 1391(5)

C(32)-C(33) 1392(6)

C(33)-C(34) 1377(7)

C(34)-C(35) 1377(6)

C(8)-C(7)-P(1) 1204(3)

C(12)-C(7)-P(1) 1209(3)

C(9)-C(8)-C(7) 1203(4)

C(8)-C(9)-C(10) 1202(5)

C(9)-C(10)-C(11) 1199(5)

C(12)-C(11)-C(10) 1202(4)

C(11)-C(12)-C(7) 1205(4)

C(14)-C(13)-C(18) 1191(3)

C(14)-C(13)-P(1) 1215(3)

C(18)-C(13)-P(1) 1194(3)

C(13)-C(14)-C(15) 1204(4)

C(16)-C(15)-C(14) 1202(4)

C(15)-C(16)-C(17) 1202(4)

C(16)-C(17)-C(18) 1196(4)

C(13)-C(18)-C(17) 1204(4)

C(24)-C(19)-C(20) 1194(4)

C(24)-C(19)-P(1) 1224(3)

C(20)-C(19)-P(1) 1182(3)

C(19)-C(20)-C(21) 1209(5)

C(22)-C(21)-C(20) 1197(5)

C(23)-C(22)-C(21) 1201(5)

C(22)-C(23)-C(24) 1207(5)

C(19)-C(24)-C(23) 1192(5)

C(30)-C(25)-C(26) 1191(4)

C(30)-C(25)-P(2) 1230(3)

C(26)-C(25)-P(2) 1176(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1197(5)

C(29)-C(28)-C(27) 1206(4)

C(28)-C(29)-C(30) 1204(5)

C(25)-C(30)-C(29) 1196(4)

C(32)-C(31)-C(36) 1189(4)

C(32)-C(31)-P(2) 1257(3)

C(36)-C(31)-P(2) 1153(3)

C(31)-C(32)-C(33) 1198(4)

C(34)-C(33)-C(32) 1207(4)

C(35)-C(34)-C(33) 1198(4)

C(34)-C(35)-C(36) 1200(4)

C(35)-C(36)-C(31) 1207(4)

C(42)-C(37)-C(38) 1184(4)

C(42)-C(37)-P(2) 1189(3)

C(38)-C(37)-P(2) 1227(3)

C(39)-C(38)-C(37) 1197(5)

C(40)-C(39)-C(38) 1206(5)

C(39)-C(40)-C(41) 1208(5)

C(40)-C(41)-C(42) 1197(5)

218

C(35)-C(36) 1387(6)

C(37)-C(42) 1385(6)

C(37)-C(38) 1399(6)

C(38)-C(39) 1392(6)

C(39)-C(40) 1360(8)

C(40)-C(41) 1361(8)

C(41)-C(42) 1394(7)

P(10)-F(14) 1578(10)

P(10)-F(13) 1579(10)

P(10)-F(16) 1597(10)

P(10)-F(12) 1598(10)

P(10)-F(15) 1599(10)

P(10)-F(11) 1614(10)

P(10)-F(11) 1588(13)

P(10)-F(13) 1591(13)

P(10)-F(14) 1592(13)

P(10)-F(12) 1593(13)

P(10)-F(16) 1595(13)

P(10)-F(15) 1598(13)

P(20)-F(25) 1551(11)

P(20)-F(24) 1557(12)

P(20)-F(26) 1563(11)

P(20)-F(22) 1566(11)

P(20)-F(21) 1575(11)

P(20)-F(23) 1585(11)

P(20)-F(23) 1521(11)

P(20)-F(21) 1545(11)

P(20)-F(26) 1559(11)

P(20)-F(24) 1560(11)

P(20)-F(22) 1585(11)

P(20)-F(25) 1628(11)

P(2)-Pd(1)-P(1) 9715(3)

P(2)-Pd(1)-S(1) 9505(3)

P(1)-Pd(1)-S(1) 16705(3)

P(2)-Pd(1)-S(3) 16837(3)

P(1)-Pd(1)-S(3) 9298(3)

S(1)-Pd(1)-S(3) 7536(3)

C(7)-P(1)-C(13) 10326(17)

C(7)-P(1)-C(19) 10743(19)

C(13)-P(1)-C(19) 10434(17)

C(7)-P(1)-Pd(1) 11069(13)

C(13)-P(1)-Pd(1) 12157(12)

C(19)-P(1)-Pd(1) 10864(13)

C(25)-P(2)-C(37) 10169(18)

C(25)-P(2)-C(31) 11326(17)

C(37)-P(2)-C(31) 10528(17)

C(25)-P(2)-Pd(1) 11377(13)

C(37)-P(2)-Pd(1) 11311(12)

C(31)-P(2)-Pd(1) 10929(13)

C(2)-S(1)-Pd(1) 8589(12)

N(4)-C(2)-S(3) 1233(3)

N(4)-C(2)-S(1) 1239(3)

S(3)-C(2)-S(1) 11276(19)

C(2)-S(3)-Pd(1) 8590(13)

C(2)-N(4)-C(5) 1234(3)

C(2)-N(4)-C(6) 1228(3)

C(5)-N(4)-C(6) 1133(3)

N(4)-C(5)-C(6)1 1090(3)

N(4)-C(6)-C(5)1 1087(3)

C(8)-C(7)-C(12) 1188(4)

C(37)-C(42)-C(41) 1208(4)

F(14)-P(10)-F(13) 910(7)

F(14)-P(10)-F(16) 912(6)

F(13)-P(10)-F(16) 912(6)

F(14)-P(10)-F(12) 1781(8)

F(13)-P(10)-F(12) 901(7)

F(16)-P(10)-F(12) 904(7)

F(14)-P(10)-F(15) 902(7)

F(13)-P(10)-F(15) 1783(8)

F(16)-P(10)-F(15) 901(7)

F(12)-P(10)-F(15) 886(7)

F(14)-P(10)-F(11) 901(7)

F(13)-P(10)-F(11) 894(7)

F(16)-P(10)-F(11) 1785(9)

F(12)-P(10)-F(11) 883(6)

F(15)-P(10)-F(11) 893(6)

F(11)-P(10)-F(13) 904(8)

F(11)-P(10)-F(14) 902(8)

F(13)-P(10)-F(14) 903(8)

F(11)-P(10)-F(12) 902(8)

F(13)-P(10)-F(12) 901(8)

F(14)-P(10)-F(12) 1795(11)

F(11)-P(10)-F(16) 1794(11)

F(13)-P(10)-F(16) 902(8)

F(14)-P(10)-F(16) 899(8)

F(12)-P(10)-F(16) 897(8)

F(11)-P(10)-F(15) 898(8)

F(13)-P(10)-F(15) 1798(12)

F(14)-P(10)-F(15) 899(8)

F(12)-P(10)-F(15) 897(8)

F(16)-P(10)-F(15) 896(8)

F(25)-P(20)-F(24) 911(7)

F(25)-P(20)-F(26) 923(7)

F(24)-P(20)-F(26) 911(7)

F(25)-P(20)-F(22) 916(7)

F(24)-P(20)-F(22) 1766(10)

F(26)-P(20)-F(22) 908(7)

F(25)-P(20)-F(21) 899(7)

F(24)-P(20)-F(21) 902(8)

F(26)-P(20)-F(21) 1774(9)

F(22)-P(20)-F(21) 878(7)

F(25)-P(20)-F(23) 1786(10)

F(24)-P(20)-F(23) 894(7)

F(26)-P(20)-F(23) 890(7)

F(22)-P(20)-F(23) 879(7)

F(21)-P(20)-F(23) 888(7)

F(23)-P(20)-F(21) 941(7)

F(23)-P(20)-F(26) 932(7)

F(21)-P(20)-F(26) 1724(8)

F(23)-P(20)-F(24) 939(7)

F(21)-P(20)-F(24) 907(7)

F(26)-P(20)-F(24) 910(7)

F(23)-P(20)-F(22) 931(7)

F(21)-P(20)-F(22) 887(7)

F(26)-P(20)-F(22) 886(7)

F(24)-P(20)-F(22) 1730(8)

F(23)-P(20)-F(25) 1771(9)

F(21)-P(20)-F(25) 878(7)

F(26)-P(20)-F(25) 849(7)

F(24)-P(20)-F(25) 883(7)

F(22)-P(20)-F(25) 847(6)

219


Table 1 Crystal data and structure refinement for JWE1605 (26)






Crystal system space group Monoclinic Ia


b = 1085381(18) Aring = 1065109(16)deg

c = 267343(4) Aring = 90deg




F(000) 4112

Crystal colour morphology Yellow tablets







220







Absolute structure parameter 0455(8)



Table 2 Bond lengths [Aring] and angles [deg] for JWE1605 (26)

Pd(1)-P(2) 22811(15)

Pd(1)-S(1) 23190(15)

Pd(1)-P(1) 23297(15)

Pd(1)-S(3) 23720(16)

Pd(2)-P(4) 22915(17)

Pd(2)-S(9) 23180(15)

Pd(2)-P(3) 23298(16)

Pd(2)-S(10) 23735(17)

P(1)-C(37) 1820(7)

P(1)-C(25) 1826(7)

P(1)-C(31) 1832(7)

P(2)-C(43) 1814(6)

P(2)-C(49) 1820(6)

P(2)-C(55) 1826(7)

P(3)-C(61) 1832(9)

P(3)-C(67) 1832(7)

P(3)-C(73) 1837(7)

P(4)-C(85) 1815(7)

P(4)-C(79) 1829(7)

P(4)-C(91) 1833(6)

S(1)-C(2) 1715(7)

C(2)-N(4) 1323(8)

C(2)-S(3) 1718(6)

N(4)-C(5) 1470(8)

N(4)-C(11) 1475(8)

C(5)-C(6) 1518(8)

C(6)-N(7) 1487(8)

N(7)-C(8) 1316(9)

N(7)-C(18) 1463(9)

C(8)-S(9) 1722(7)

C(8)-S(10) 1727(7)

C(11)-C(12) 1500(9)

C(12)-C(13) 1376(11)

C(12)-C(17) 1378(10)

C(13)-C(14) 1385(12)

C(14)-C(15) 1393(14)

C(15)-C(16) 1363(14)

C(16)-C(17) 1377(13)

C(18)-C(19) 1510(11)

C(19)-C(24) 1374(12)

C(19)-C(20) 1406(11)

C(20)-C(21) 1390(15)

C(21)-C(22) 1352(18)

C(22)-C(23) 1395(16)

C(79)-P(4)-Pd(2) 1116(2)

C(91)-P(4)-Pd(2) 1124(20

C(2)-S(1)-Pd(1) 859(2)

N(4)-C(2)-S(1) 1227(5)

N(4)-C(2)-S(3) 1240(5)

S(1)-C(2)-S(3) 1132(4)

C(2)-S(3)-Pd(1) 842(2)

C(2)-N(4)-C(5) 1214(5)

C(2)-N(4)-C(11) 1207(5)

C(5)-N(4)-C(11) 1176(5)

N(4)-C(5)-C(6) 1104(5)

N(7)-C(6)-C(5) 1085(5)

C(8)-N(7)-C(18) 1229(6)

C(8)-N(7)-C(6) 1194(6)

C(18)-N(7)-C(6) 1177(5)

N(7)-C(8)-S(9) 1234(5)

N(7)-C(8)-S(10) 1247(5)

S(9)-C(8)-S(10) 1119(4)

C(8)-S(9)-Pd(2) 873(2)

C(8)-S(10)-Pd(2) 854(2)

N(4)-C(11)-C(12) 1154(5)

C(13)-C(12)-C(17) 1187(7)

C(13)-C(12)-C(11) 1218(6)

C(17)-C(12)-C(11) 1193(6)

C(12)-C(13)-C(14) 1206(8)

C(13)-C(14)-C(15) 1203(9)

C(16)-C(15)-C(14) 1185(8)

C(15)-C(16)-C(17) 1214(8)

C(16)-C(17)-C(12) 1206(8)

N(7)-C(18)-C(19) 1127(6)

C(24)-C(19)-C(20) 1180(8)

C(24)-C(19)-C(18) 1234(7)

C(20)-C(19)-C(18) 1185(8)

C(21)-C(20)-C(19) 1189(10)

C(22)-C(21)-C(20) 1229(9)

C(21)-C(22)-C(23) 1187(10)

C(24)-C(23)-C(22) 1193(10)

C(19)-C(24)-C(23) 1222(8)

C(30)-C(25)-C(26) 1194(6)

C(30)-C(25)-P(1) 1211(5)

C(26)-C(25)-P(1) 1194(5)

C(27)-C(26)-C(25) 1195(7)

C(28)-C(27)-C(26) 1206(7)

221

C(23)-C(24) 1389(12)

C(25)-C(30) 1387(10)

C(25)-C(26) 1396(9)

C(26)-C(27) 1392(10)

C(27)-C(28) 1372(12)

C(28)-C(29) 1373(12)

C(29)-C(30) 1391(10)

C(31)-C(32) 1392(9)

C(31)-C(36) 1404(9)

C(32)-C(33) 1390(10)

C(33)-C(34) 1390(13)

C(34)-C(35) 1368(13)

C(35)-C(36) 1396(11)

C(37)-C(42) 1387(10)

C(37)-C(38) 1393(10)

C(38)-C(39) 1387(10)

C(39)-C(40) 1361(12)

C(40)-C(41) 1385(12)

C(41)-C(42) 1390(10)

C(43)-C(48) 1396(10)

C(43)-C(44) 1400(10)

C(44)-C(45) 1370(10)

C(45)-C(46) 1379(12)

C(46)-C(47) 1382(13)

C(47)-C(48) 1400(11)

C(49)-C(54) 1384(11)

C(49)-C(50) 1400(10)

C(50)-C(51) 1380(9)

C(51)-C(52) 1377(14)

C(52)-C(53) 1362(15)

C(53)-C(54) 1399(11)

C(55)-C(60) 1380(9)

C(55)-C(56) 1407(9)

C(56)-C(57) 1370(10)

C(57)-C(58) 1381(11)

C(58)-C(59) 1402(12)

C(59)-C(60) 1373(11)

C(61)-C(62) 1375(11)

C(61)-C(66) 1404(11)

C(62)-C(63) 1395(11)

C(63)-C(64) 1402(14)

C(64)-C(65) 1358(16)

C(65)-C(66) 1377(14)

C(67)-C(68) 1379(11)

C(67)-C(72) 1401(11)

C(68)-C(69) 1386(11)

C(69)-C(70) 1394(14)

C(70)-C(71) 1376(15)

C(71)-C(72) 1391(12)

C(73)-C(78) 1391(11)

C(73)-C(74) 1400(9)

C(74)-C(75) 1393(13)

C(75)-C(76) 1391(14)

C(76)-C(77) 1394(12)

C(77)-C(78) 1384(13)

C(79)-C(84) 1376(11)

C(79)-C(80) 1402(10)

C(80)-C(81) 1399(10)

C(81)-C(82) 1371(13)

C(82)-C(83) 1384(12)

C(83)-C(84) 1379(10)

C(27)-C(28)-C(29) 1202(7)

C(28)-C(29)-C(30) 1202(7)

C(25)-C(30)-C(29) 1201(7)

C(32)-C(31)-C(36) 1189(6)

C(32)-C(31)-P(1) 1203(5)

C(36)-C(31)-P(1) 1208(5)

C(33)-C(32)-C(31) 1208(7)

C(32)-C(33)-C(34) 1204(7)

C(35)-C(34)-C(33) 1187(7)

C(34)-C(35)-C(36) 1224(7)

C(35)-C(36)-C(31) 1188(7)

C(42)-C(37)-C(38) 1181(6)

C(42)-C(37)-P(1) 1194(5)

C(38)-C(37)-P(1) 1224(5)

C(39)-C(38)-C(37) 1210(7)

C(40)-C(39)-C(38) 1202(7)

C(39)-C(40)-C(41) 1200(7)

C(40)-C(41)-C(42) 1200(7)

C(37)-C(42)-C(41) 1206(7)

C(48)-C(43)-C(44) 1199(6)

C(48)-C(43)-P(2) 1250(6)

C(44)-C(43)-P(2) 1151(5)

C(45)-C(44)-C(43) 1201(7)

C(44)-C(45)-C(46) 1205(7)

C(45)-C(46)-C(47) 1202(7)

C(46)-C(47)-C(48) 1204(7)

C(43)-C(48)-C(47) 1189(8)

C(54)-C(49)-C(50) 1205(6)

C(54)-C(49)-P(2) 1209(6)

C(50)-C(49)-P(2) 1185(5)

C(51)-C(50)-C(49) 1197(7)

C(52)-C(51)-C(50) 1198(8)

C(53)-C(52)-C(51) 1205(7)

C(52)-C(53)-C(54) 1213(8)

C(49)-C(54)-C(53) 1181(8)

C(60)-C(55)-C(56) 1188(6)

C(60)-C(55)-P(2) 1235(5)

C(56)-C(55)-P(2) 1177(5)

C(57)-C(56)-C(55) 1198(6)

C(56)-C(57)-C(58) 1213(7)

C(57)-C(58)-C(59) 1190(7)

C(60)-C(59)-C(58) 1197(7)

C(59)-C(60)-C(55) 1213(7)

C(62)-C(61)-C(66) 1196(8)

C(62)-C(61)-P(3) 1193(6)

C(66)-C(61)-P(3) 1208(7)

C(61)-C(62)-C(63) 1218(8)

C(62)-C(63)-C(64) 1176(9)

C(65)-C(64)-C(63) 1203(8)

C(64)-C(65)-C(66) 1224(9)

C(65)-C(66)-C(61) 1183(9)

C(68)-C(67)-C(72) 1195(7)

C(68)-C(67)-P(3) 1198(6)

C(72)-C(67)-P(3) 1204(6)

C(67)-C(68)-C(69) 1210(8)

C(68)-C(69)-C(70) 1192(8)

C(71)-C(70)-C(69) 1205(8)

C(70)-C(71)-C(72) 1202(9)

C(71)-C(72)-C(67) 1196(9)

C(78)-C(73)-C(74) 1186(7)

C(78)-C(73)-P(3) 1212(5)

222

C(85)-C(90) 1379(11)

C(85)-C(86) 1391(10)

C(86)-C(87) 1391(10)

C(87)-C(88) 1387(15)

C(88)-C(89) 1371(14)

C(89)-C(90) 1390(11)

C(91)-C(92) 1379(9)

C(91)-C(96) 1387(9)

C(92)-C(93) 1393(11)

C(93)-C(94) 1368(12)

C(94)-C(95) 1397(11)

C(95)-C(96) 1375(10)

P(10)-F(11) 1550(6)

P(10)-F(15) 1576(5)

P(10)-F(13) 1584(6)

P(10)-F(14) 1590(6)

P(10)-F(12) 1600(5)

P(10)-F(16) 1600(7)

P(20)-F(26) 1543(8)

P(20)-F(21) 1565(8)

P(20)-F(25) 1565(5)

P(20)-F(22) 1568(6)

P(20)-F(24) 1571(6)

P(20)-F(23) 1581(5)

P(2)-Pd(1)-S(1) 9072(5)

P(2)-Pd(1)-P(1) 9793(6)

S(1)-Pd(1)-P(1) 16824(5)

P(2)-Pd(1)-S(3) 16550(6)

S(1)-Pd(1)-S(3) 7528(5)

P(1)-Pd(1)-S(3) 9647(5)

P(4)-Pd(2)-S(9) 9136(5)

P(4)-Pd(2)-P(3) 9795(6)

S(9)-Pd(2)-P(3) 17015(6)

P(4)-Pd(2)-S(10) 16641(6)

S(9)-Pd(2)-S(10) 7505(5)

P(3)-Pd(2)-S(10) 9564(6)

C(37)-P(1)-C(25) 1061(3)

C(37)-P(1)-C(31) 1040(3)

C(25)-P(1)-C(31) 1013(3)

C(37)-P(1)-Pd(1) 1142(2)

C(25)-P(1)-Pd(1) 1091(2)

C(31)-P(1)-Pd(1) 1205(2)

C(43)-P(2)-C(49) 1115(3)

C(43)-P(2)-C(55) 1047(3)

C(49)-P(2)-C(55) 1020(3)

C(43)-P(2)-Pd(1) 1110(2)

C(49)-P(2)-Pd(1) 1132(2)

C(55)-P(2)-Pd(1) 1139(2)

C(61)-P(3)-C(67) 1067(4)

C(61)-P(3)-C(73) 1028(4)

C(67)-P(3)-C(73) 1047(4)

C(61)-P(3)-Pd(2) 1087(3)

C(67)-P(3)-Pd(2) 1122(3)

C(73)-P(3)-Pd(2) 1207(2)

C(85)-P(4)-C(79) 1107(3)

C(85)-P(4)-C(91) 1023(3)

C(79)-P(4)-C(91) 1052(3)

C(85)-P(4)-Pd(2) 1139(3)

C(74)-C(73)-P(3) 1202(6)

C(75)-C(74)-C(73) 1202(8)

C(76)-C(75)-C(74) 1199(7)

C(75)-C(76)-C(77) 1207(8)

C(78)-C(77)-C(76) 1186(9)

C(77)-C(78)-C(73) 1220(7)

C(84)-C(79)-C(80) 1205(6)

C(84)-C(79)-P(4) 1249(5)

C(80)-C(79)-P(4) 1146(5)

C(81)-C(80)-C(79) 1181(7)

C(82)-C(81)-C(80) 1211(7)

C(81)-C(82)-C(83) 1197(7)

C(84)-C(83)-C(82) 1203(7)

C(79)-C(84)-C(83) 1201(7)

C(90)-C(85)-C(86) 1198(7)

C(90)-C(85)-P(4) 1219(6)

C(86)-C(85)-P(4) 1183(6)

C(87)-C(86)-C(85) 1201(8)

C(88)-C(87)-C(86) 1198(8)

C(89)-C(88)-C(87) 1195(7)

C(88)-C(89)-C(90) 1212(9)

C(85)-C(90)-C(89) 1195(8)

C(92)-C(91)-C(96) 1197(6)

C(92)-C(91)-P(4) 1225(5)

C(96)-C(91)-P(4) 1177(5)

C(91)-C(92)-C(93) 1198(7)

C(94)-C(93)-C(92) 1209(7)

C(93)-C(94)-C(95) 1189(7)

C(96)-C(95)-C(94) 1207(7)

C(95)-C(96)-C(91) 1201(6)

F(11)-P(10)-F(15) 920(4)

F(11)-P(10)-F(13) 909(4)

F(15)-P(10)-F(13) 1769(4)

F(11)-P(10)-F(14) 909(4)

F(15)-P(10)-F(14) 889(3)

F(13)-P(10)-F(14) 921(4)

F(11)-P(10)-F(12) 902(4)

F(15)-P(10)-F(12) 897(3)

F(13)-P(10)-F(12) 892(3)

F(14)-P(10)-F(12) 1783(3)

F(11)-P(10)-F(16) 1792(4)

F(15)-P(10)-F(16) 885(4)

F(13)-P(10)-F(16) 885(4)

F(14)-P(10)-F(16) 897(4)

F(12)-P(10)-F(16) 892(3)

F(26)-P(20)-F(21) 1790(6)

F(26)-P(20)-F(25) 893(5)

F(21)-P(20)-F(25) 897(5)

F(26)-P(20)-F(22) 932(6)

F(21)-P(20)-F(22) 865(6)

F(25)-P(20)-F(22) 894(4)

F(26)-P(20)-F(24) 875(6)

F(21)-P(20)-F(24) 928(6)

F(25)-P(20)-F(24) 907(3)

F(22)-P(20)-F(24) 1794(6)

F(26)-P(20)-F(23) 889(4)

F(21)-P(20)-F(23) 921(4)

F(25)-P(20)-F(23) 1780(5)

F(22)-P(20)-F(23) 899(3)

F(24)-P(20)-F(23) 901(3)

223





224

Table 1 Crystal data and structure refinement for JWE1613(36-A AND 36-B)


Formula C44 H48 N O3 P2 Pd S2 Si F6 P

05(C H2 Cl2)




Crystal system space group Monoclinic I2a


b = 192506(5) Aring = 970520(16)deg

c = 494978(9) Aring = 90deg




F(000) 8880
















225


Pd(1A)-P(2A) 23045(9)

Pd(1A)-P(1A) 23091(9)

Pd(1A)-S(1A) 23294(9)

Pd(1A)-S(3A) 23458(9)

P(1A)-C(22A) 1817(3)

P(1A)-C(28A) 1820(3)

P(1A)-C(16A) 1821(3)

P(1A)-C(22) 1838(8)

P(2A)-C(46A) 1815(4)

P(2A)-C(34A) 1823(4)

P(2A)-C(40A) 1837(4)

P(2A)-C(40) 1843(6)

S(1A)-C(2A) 1726(3)

C(2A)-N(4A) 1306(4)

C(2A)-S(3A) 1717(4)

N(4A)-C(5A) 1467(5)

N(4A)-C(15A) 1467(4)

C(5A)-C(6A) 1528(5)

C(6A)-C(7A) 1512(5)

C(7A)-Si(8A) 1718(5)

C(7A)-Si(8) 2004(6)

Si(8A)-O(13A) 1602(5)

Si(8A)-O(9A) 1629(6)

Si(8A)-O(11A) 1634(5)

O(9A)-C(10A) 1436(8)

O(11A)-C(12A) 1401(8)

O(13A)-C(14A) 1388(9)

Si(8)-O(9) 1606(8)

Si(8)-O(11) 1618(8)

Si(8)-O(13) 1633(8)

O(9)-C(10) 1422(12)

O(11)-C(12) 1418(13)

O(13)-C(14) 1462(12)

C(16A)-C(21A) 1387(5)

C(16A)-C(17A) 1391(5)

C(17A)-C(18A) 1379(5)

C(18A)-C(19A) 1378(6)

C(19A)-C(20A) 1359(6)

C(20A)-C(21A) 1395(5)

C(22A)-C(23A) 13900

C(22A)-C(27A) 13900

C(23A)-C(24A) 13900

C(24A)-C(25A) 13900

C(25A)-C(26A) 13900

C(26A)-C(27A) 13900

C(22)-C(23) 13900

C(22)-C(27) 13900

C(23)-C(24) 13900

C(24)-C(25) 13900

C(25)-C(26) 13900

C(26)-C(27) 13900

C(28A)-C(33A) 1385(5)

C(28A)-C(29A) 1395(5)

C(29A)-C(30A) 1377(5)

C(30A)-C(31A) 1367(6)

C(31A)-C(32A) 1380(6)

C(32A)-C(33A) 1387(5)

C(34A)-C(35A) 1377(5)

C(34A)-C(39A) 1394(5)

O(13)-Si(8)-C(7A) 1101(4)

C(10)-O(9)-Si(8) 1212(8)

C(12)-O(11)-Si(8) 1233(9)

C(14)-O(13)-Si(8) 1224(8)

C(21A)-C(16A)-C(17A) 1189(3)

C(21A)-C(16A)-P(1A) 1232(3)

C(17A)-C(16A)-P(1A) 1178(3)

C(18A)-C(17A)-C(16A) 1206(4)

C(19A)-C(18A)-C(17A) 1198(4)

C(20A)-C(19A)-C(18A) 1205(4)

C(19A)-C(20A)-C(21A) 1203(4)

C(16A)-C(21A)-C(20A) 1198(4)

C(23A)-C(22A)-C(27A) 1200

C(23A)-C(22A)-P(1A) 1187(3)

C(27A)-C(22A)-P(1A) 1213(3)

C(24A)-C(23A)-C(22A) 1200

C(25A)-C(24A)-C(23A) 1200

C(24A)-C(25A)-C(26A) 1200

C(27A)-C(26A)-C(25A) 1200

C(26A)-C(27A)-C(22A) 1200

C(23)-C(22)-C(27) 1200

C(23)-C(22)-P(1A) 1215(7)

C(27)-C(22)-P(1A) 1185(7)

C(24)-C(23)-C(22) 1200

C(25)-C(24)-C(23) 1200

C(24)-C(25)-C(26) 1200

C(25)-C(26)-C(27) 1200

C(26)-C(27)-C(22) 1200

C(33A)-C(28A)-C(29A) 1187(3)

C(33A)-C(28A)-P(1A) 1220(3)

C(29A)-C(28A)-P(1A) 1193(3)

C(30A)-C(29A)-C(28A) 1205(4)

C(31A)-C(30A)-C(29A) 1205(4)

C(30A)-C(31A)-C(32A) 1199(4)

C(31A)-C(32A)-C(33A) 1202(4)

C(28A)-C(33A)-C(32A) 1202(4)

C(35A)-C(34A)-C(39A) 1196(3)

C(35A)-C(34A)-P(2A) 1178(3)

C(39A)-C(34A)-P(2A) 1226(3)

C(34A)-C(35A)-C(36A) 1199(4)

C(37A)-C(36A)-C(35A) 1198(5)

C(38A)-C(37A)-C(36A) 1203(4)

C(37A)-C(38A)-C(39A) 1204(4)

C(38A)-C(39A)-C(34A) 1200(4)

C(41A)-C(40A)-C(45A) 1200

C(41A)-C(40A)-P(2A) 1219(4)

C(45A)-C(40A)-P(2A) 1181(4)

C(42A)-C(41A)-C(40A) 1200

C(41A)-C(42A)-C(43A) 1200

C(42A)-C(43A)-C(44A) 1200

C(45A)-C(44A)-C(43A) 1200

C(44A)-C(45A)-C(40A) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2A) 1242(5)

C(45)-C(40)-P(2A) 1152(6)

C(40)-C(41)-C(42) 1200

C(43)-C(42)-C(41) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

226

C(35A)-C(36A) 1394(6)

C(36A)-C(37A) 1377(7)

C(37A)-C(38A) 1369(7)

C(38A)-C(39A) 1374(5)

C(40A)-C(41A) 13900

C(40A)-C(45A) 13900

C(41A)-C(42A) 13900

C(42A)-C(43A) 13900

C(43A)-C(44A) 13900

C(44A)-C(45A) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46A)-C(51A) 1374(5)

C(46A)-C(47A) 1390(5)

C(47A)-C(48A) 1378(5)

C(48A)-C(49A) 1366(6)

C(49A)-C(50A) 1372(6)

C(50A)-C(51A) 1397(5)

Pd(1B)-P(2B) 22980(9)

Pd(1B)-P(1B) 23261(9)

Pd(1B)-S(1B) 23293(9)

Pd(1B)-S(3B) 23476(10)

P(1B)-C(28) 1800(6)

P(1B)-C(22B) 1817(3)

P(1B)-C(16B) 1822(3)

P(1B)-C(28B) 1853(3)

P(2B)-C(46B) 1725(3)

P(2B)-C(40) 1811(7)

P(2B)-C(34B) 1819(4)

P(2B)-C(40B) 1849(4)

P(2B)-C(46) 1911(5)

S(1B)-C(2B) 1719(4)

C(2B)-N(4B) 1312(5)

C(2B)-S(3B) 1722(4)

N(4B)-C(15B) 1434(7)

N(4B)-C(5) 1434(11)

N(4B)-C(5B) 1523(9)

N(4B)-C(15) 1553(9)

C(5B)-C(6B) 1527(11)

C(6B)-C(7B) 1513(9)

C(7B)-Si(8B) 1842(7)

Si(8B)-O(11B) 1612(6)

Si(8B)-O(9B) 1626(8)

Si(8B)-O(13B) 1629(5)

O(9B)-C(10B) 1426(12)

O(11B)-C(12B) 1431(10)

O(13B)-C(14B) 1383(10)

C(5)-C(6) 1496(12)

C(6)-C(7) 1488(10)

C(7)-Si(8) 1861(8)

Si(8)-O(9) 1577(9)

Si(8)-O(13) 1600(8)

Si(8)-O(11) 1640(8)

O(9)-C(10) 1372(13)

O(11)-C(12) 1411(10)

O(13)-C(14) 1388(12)

C(16B)-C(17B) 1369(5)

C(44)-C(45)-C(40) 1200

C(51A)-C(46A)-C(47A) 1192(3)

C(51A)-C(46A)-P(2A) 1215(3)

C(47A)-C(46A)-P(2A) 1194(3)

C(48A)-C(47A)-C(46A) 1205(4)

C(49A)-C(48A)-C(47A) 1200(4)

C(48A)-C(49A)-C(50A) 1203(4)

C(49A)-C(50A)-C(51A) 1200(4)

C(46A)-C(51A)-C(50A) 1200(4)

P(2B)-Pd(1B)-P(1B) 9991(3)

P(2B)-Pd(1B)-S(1B) 9282(3)

P(1B)-Pd(1B)-S(1B) 16611(3)

P(2B)-Pd(1B)-S(3B) 16751(4)

P(1B)-Pd(1B)-S(3B) 9257(3)

S(1B)-Pd(1B)-S(3B) 7472(4)

C(28)-P(1B)-C(22B) 1115(3)

C(28)-P(1B)-C(16B) 1024(4)

C(22B)-P(1B)-C(16B) 10549(16)

C(22B)-P(1B)-C(28B) 1015(2)

C(16B)-P(1B)-C(28B) 1044(2)

C(28)-P(1B)-Pd(1B) 1174(3)

C(22B)-P(1B)-Pd(1B) 10938(12)

C(16B)-P(1B)-Pd(1B) 10984(12)

C(28B)-P(1B)-Pd(1B) 1245(2)

C(46B)-P(2B)-C(34B) 1031(2)

C(40)-P(2B)-C(34B) 1057(4)

C(46B)-P(2B)-C(40B) 1035(3)

C(34B)-P(2B)-C(40B) 1050(2)

C(40)-P(2B)-C(46) 994(5)

C(34B)-P(2B)-C(46) 1146(3)

C(46B)-P(2B)-Pd(1B) 12210(18)

C(40)-P(2B)-Pd(1B) 1163(4)

C(34B)-P(2B)-Pd(1B) 11240(13)

C(40B)-P(2B)-Pd(1B) 1092(3)

C(46)-P(2B)-Pd(1B) 10795(19)

C(2B)-S(1B)-Pd(1B) 8727(14)

N(4B)-C(2B)-S(1B) 1242(3)

N(4B)-C(2B)-S(3B) 1247(3)

S(1B)-C(2B)-S(3B) 1111(2)

C(2B)-S(3B)-Pd(1B) 8661(13)

C(2B)-N(4B)-C(15B) 1252(5)

C(2B)-N(4B)-C(5) 1241(9)

C(2B)-N(4B)-C(5B) 1207(6)

C(15B)-N(4B)-C(5B) 1135(6)

C(2B)-N(4B)-C(15) 1156(5)

C(5)-N(4B)-C(15) 1200(9)

N(4B)-C(5B)-C(6B) 1098(7)

C(7B)-C(6B)-C(5B) 1152(7)

C(6B)-C(7B)-Si(8B) 1124(5)

O(11B)-Si(8B)-O(9B) 1112(4)

O(11B)-Si(8B)-O(13B) 1081(3)

O(9B)-Si(8B)-O(13B) 1049(4)

O(11B)-Si(8B)-C(7B) 1091(3)

O(9B)-Si(8B)-C(7B) 1110(4)

O(13B)-Si(8B)-C(7B) 1124(3)

C(10B)-O(9B)-Si(8B) 1228(7)

C(12B)-O(11B)-Si(8B) 1249(6)

C(14B)-O(13B)-Si(8B) 1273(7)

N(4B)-C(5)-C(6) 1110(10)

C(7)-C(6)-C(5) 1143(10)

C(6)-C(7)-Si(8) 1165(7)

227

C(16B)-C(21B) 1378(5)

C(17B)-C(18B) 1386(5)

C(18B)-C(19B) 1359(6)

C(19B)-C(20B) 1360(6)

C(20B)-C(21B) 1384(5)

C(22B)-C(23B) 1383(5)

C(22B)-C(27B) 1385(5)

C(23B)-C(24B) 1384(6)

C(24B)-C(25B) 1362(7)

C(25B)-C(26B) 1364(7)

C(26B)-C(27B) 1373(5)

C(28B)-C(29B) 13900

C(28B)-C(33B) 13900

C(29B)-C(30B) 13900

C(30B)-C(31B) 13900

C(31B)-C(32B) 13900

C(32B)-C(33B) 13900

C(28)-C(29) 13900

C(28)-C(33) 13900

C(29)-C(30) 13900

C(30)-C(31) 13900

C(31)-C(32) 13900

C(32)-C(33) 13900

C(34B)-C(35B) 1381(6)

C(34B)-C(39B) 1396(6)

C(35B)-C(36B) 1394(6)

C(36B)-C(37B) 1388(7)

C(37B)-C(38B) 1363(8)

C(38B)-C(39B) 1383(7)

C(40B)-C(41B) 13900

C(40B)-C(45B) 13900

C(41B)-C(42B) 13900

C(42B)-C(43B) 13900

C(43B)-C(44B) 13900

C(44B)-C(45B) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46B)-C(47B) 13900

C(46B)-C(51B) 13900

C(47B)-C(48B) 13900

C(48B)-C(49B) 13900

C(49B)-C(50B) 13900

C(50B)-C(51B) 13900

C(46)-C(47) 13900

C(46)-C(51) 13900

C(47)-C(48) 13900

C(48)-C(49) 13900

C(49)-C(50) 13900

C(50)-C(51) 13900

P(60)-F(65) 1563(4)

P(60)-F(62) 1570(4)

P(60)-F(64) 1572(4)

P(60)-F(63) 1581(4)

P(60)-F(66) 1592(4)

P(60)-F(61) 1601(4)

P(60)-F(62) 1557(11)

P(60)-F(64) 1562(11)

O(9)-Si(8)-O(13) 1091(6)

O(9)-Si(8)-O(11) 1115(5)

O(13)-Si(8)-O(11) 1066(4)

O(9)-Si(8)-C(7) 1042(6)

O(13)-Si(8)-C(7) 1119(4)

O(11)-Si(8)-C(7) 1135(4)

C(10)-O(9)-Si(8) 1269(9)

C(12)-O(11)-Si(8) 1245(7)

C(14)-O(13)-Si(8) 1277(8)

C(17B)-C(16B)-C(21B) 1181(3)

C(17B)-C(16B)-P(1B) 1190(3)

C(21B)-C(16B)-P(1B) 1229(3)

C(16B)-C(17B)-C(18B) 1213(4)

C(19B)-C(18B)-C(17B) 1199(4)

C(18B)-C(19B)-C(20B) 1197(4)

C(19B)-C(20B)-C(21B) 1206(4)

C(16B)-C(21B)-C(20B) 1204(4)

C(23B)-C(22B)-C(27B) 1181(3)

C(23B)-C(22B)-P(1B) 1225(3)

C(27B)-C(22B)-P(1B) 1194(3)

C(22B)-C(23B)-C(24B) 1204(4)

C(25B)-C(24B)-C(23B) 1204(4)

C(24B)-C(25B)-C(26B) 1198(4)

C(25B)-C(26B)-C(27B) 1203(4)

C(26B)-C(27B)-C(22B) 1209(4)

C(29B)-C(28B)-C(33B) 1200

C(29B)-C(28B)-P(1B) 1201(3)

C(33B)-C(28B)-P(1B) 1199(3)

C(28B)-C(29B)-C(30B) 1200

C(31B)-C(30B)-C(29B) 1200

C(30B)-C(31B)-C(32B) 1200

C(31B)-C(32B)-C(33B) 1200

C(32B)-C(33B)-C(28B) 1200

C(29)-C(28)-C(33) 1200

C(29)-C(28)-P(1B) 1209(5)

C(33)-C(28)-P(1B) 1190(5)

C(30)-C(29)-C(28) 1200

C(29)-C(30)-C(31) 1200

C(30)-C(31)-C(32) 1200

C(33)-C(32)-C(31) 1200

C(32)-C(33)-C(28) 1200

C(35B)-C(34B)-C(39B) 1196(4)

C(35B)-C(34B)-P(2B) 1173(3)

C(39B)-C(34B)-P(2B) 1230(4)

C(34B)-C(35B)-C(36B) 1205(4)

C(37B)-C(36B)-C(35B) 1192(5)

C(38B)-C(37B)-C(36B) 1202(5)

C(37B)-C(38B)-C(39B) 1213(5)

C(38B)-C(39B)-C(34B) 1191(5)

C(41B)-C(40B)-C(45B) 1200

C(41B)-C(40B)-P(2B) 1245(4)

C(45B)-C(40B)-P(2B) 1153(4)

C(40B)-C(41B)-C(42B) 1200

C(43B)-C(42B)-C(41B) 1200

C(44B)-C(43B)-C(42B) 1200

C(43B)-C(44B)-C(45B) 1200

C(44B)-C(45B)-C(40B) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2B) 1183(7)

C(45)-C(40)-P(2B) 1217(7)

C(42)-C(41)-C(40) 1200

228

P(60)-F(63) 1568(11)

P(60)-F(65) 1571(11)

P(60)-F(61) 1585(11)

P(60)-F(66) 1605(11)

P(70)-F(73) 1564(3)

P(70)-F(71) 1570(3)

P(70)-F(74) 1570(3)

P(70)-F(75) 1577(3)

P(70)-F(72) 1586(3)

P(70)-F(76) 1592(3)

C(80)-Cl(82) 1647(11)

C(80)-Cl(81) 1747(11)

C(90)-Cl(92) 165(5)

C(90)-Cl(91) 185(7)

P(2A)-Pd(1A)-P(1A) 10199(3)

P(2A)-Pd(1A)-S(1A) 9315(3)

P(1A)-Pd(1A)-S(1A) 16444(3)

P(2A)-Pd(1A)-S(3A) 16753(3)

P(1A)-Pd(1A)-S(3A) 8973(3)

S(1A)-Pd(1A)-S(3A) 7492(3)

C(22A)-P(1A)-C(28A) 1062(2)

C(22A)-P(1A)-C(16A) 1044(2)

C(28A)-P(1A)-C(16A) 10468(16)

C(28A)-P(1A)-C(22) 960(5)

C(16A)-P(1A)-C(22) 1101(5)

C(22A)-P(1A)-Pd(1A) 10918(18)

C(28A)-P(1A)-Pd(1A) 12376(11)

C(16A)-P(1A)-Pd(1A) 10703(12)

C(22)-P(1A)-Pd(1A) 1144(4)

C(46A)-P(2A)-C(34A) 10586(16)

C(46A)-P(2A)-C(40A) 989(3)

C(34A)-P(2A)-C(40A) 1086(3)

C(46A)-P(2A)-C(40) 1060(4)

C(34A)-P(2A)-C(40) 1032(4)

C(46A)-P(2A)-Pd(1A) 11826(12)

C(34A)-P(2A)-Pd(1A) 11366(12)

C(40A)-P(2A)-Pd(1A) 1103(3)

C(40)-P(2A)-Pd(1A) 1086(4)

C(2A)-S(1A)-Pd(1A) 8685(13)

N(4A)-C(2A)-S(3A) 1252(3)

N(4A)-C(2A)-S(1A) 1234(3)

S(3A)-C(2A)-S(1A) 1114(2)

C(2A)-S(3A)-Pd(1A) 8652(12)

C(2A)-N(4A)-C(5A) 1217(3)

C(2A)-N(4A)-C(15A) 1220(3)

C(5A)-N(4A)-C(15A) 1162(3)

N(4A)-C(5A)-C(6A) 1100(3)

C(7A)-C(6A)-C(5A) 1121(3)

C(6A)-C(7A)-Si(8A) 1149(3)

C(6A)-C(7A)-Si(8) 1142(3)

O(13A)-Si(8A)-O(9A) 1067(3)

O(13A)-Si(8A)-O(11A) 1115(3)

O(9A)-Si(8A)-O(11A) 1063(3)

O(13A)-Si(8A)-C(7A) 1115(3)

O(9A)-Si(8A)-C(7A) 1113(3)

O(11A)-Si(8A)-C(7A) 1093(3)

C(10A)-O(9A)-Si(8A) 1226(5)

C(12A)-O(11A)-Si(8A) 1220(5)

C(14A)-O(13A)-Si(8A) 1221(6)

O(9)-Si(8)-O(11) 1128(5)

C(41)-C(42)-C(43) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

C(44)-C(45)-C(40) 1200

C(47B)-C(46B)-C(51B) 1200

C(47B)-C(46B)-P(2B) 1224(3)

C(51B)-C(46B)-P(2B) 1176(3)

C(46B)-C(47B)-C(48B) 1200

C(47B)-C(48B)-C(49B) 1200

C(50B)-C(49B)-C(48B) 1200

C(49B)-C(50B)-C(51B) 1200

C(50B)-C(51B)-C(46B) 1200

C(47)-C(46)-C(51) 1200

C(47)-C(46)-P(2B) 1201(3)

C(51)-C(46)-P(2B) 1199(3)

C(48)-C(47)-C(46) 1200

C(49)-C(48)-C(47) 1200

C(50)-C(49)-C(48) 1200

C(49)-C(50)-C(51) 1200

C(50)-C(51)-C(46) 1200

F(65)-P(60)-F(62) 921(3)

F(65)-P(60)-F(64) 890(3)

F(62)-P(60)-F(64) 1789(4)

F(65)-P(60)-F(63) 1788(3)

F(62)-P(60)-F(63) 887(3)

F(64)-P(60)-F(63) 902(3)

F(65)-P(60)-F(66) 899(3)

F(62)-P(60)-F(66) 900(3)

F(64)-P(60)-F(66) 903(3)

F(63)-P(60)-F(66) 910(3)

F(65)-P(60)-F(61) 901(3)

F(62)-P(60)-F(61) 893(3)

F(64)-P(60)-F(61) 903(3)

F(63)-P(60)-F(61) 890(3)

F(66)-P(60)-F(61) 1793(4)

F(62)-P(60)-F(64) 1789(9)

F(62)-P(60)-F(63) 890(7)

F(64)-P(60)-F(63) 910(7)

F(62)-P(60)-F(65) 896(7)

F(64)-P(60)-F(65) 904(7)

F(63)-P(60)-F(65) 1783(9)

F(62)-P(60)-F(61) 904(7)

F(64)-P(60)-F(61) 907(7)

F(63)-P(60)-F(61) 901(7)

F(65)-P(60)-F(61) 909(7)

F(62)-P(60)-F(66) 901(7)

F(64)-P(60)-F(66) 888(7)

F(63)-P(60)-F(66) 893(7)

F(65)-P(60)-F(66) 897(7)

F(61)-P(60)-F(66) 1792(10)

F(73)-P(70)-F(71) 910(2)

F(73)-P(70)-F(74) 912(2)

F(71)-P(70)-F(74) 8971(19)

F(73)-P(70)-F(75) 1774(2)

F(71)-P(70)-F(75) 8995(18)

F(74)-P(70)-F(75) 913(2)

F(73)-P(70)-F(72) 898(2)

F(71)-P(70)-F(72) 9080(18)

F(74)-P(70)-F(72) 1789(2)

F(75)-P(70)-F(72) 8775(19)

F(73)-P(70)-F(76) 8966(18)

229

O(9)-Si(8)-O(13) 1017(5)

O(11)-Si(8)-O(13) 1130(5)

O(9)-Si(8)-C(7A) 1118(5)

O(11)-Si(8)-C(7A) 1074(4)

F(71)-P(70)-F(76) 1790(2)

F(74)-P(70)-F(76) 8954(17)

F(75)-P(70)-F(76) 8944(18)

F(72)-P(70)-F(76) 8994(17)

Cl(82)-C(80)-Cl(81) 1144(7)

Cl(92)-C(90)-Cl(91) 1077(16)


[(MeO)3SiCH2CH2CH22NCS2Pd(PPh3)2]PF6 (37)



Formula C49 H60 N O6 P2 Pd S2 Si2 F6 P






230

b = 147655(6) Aring = 76579(4)deg

c = 162359(7) Aring = 81131(3)deg




F(000) 1228

Crystal colour morphology Pale yellow plates
















Pd(1)-P(2) 22919(8)

Pd(1)-P(1) 23209(8)

Pd(1)-S(1) 23312(8)

Pd(1)-S(3) 23603(8)

P(1)-C(37) 1818(3)

P(1)-C(31) 1820(4)

P(1)-C(25) 1823(4)

P(2)-C(43) 1813(4)

P(2)-C(55) 1820(4)

P(2)-C(49) 1834(3)

S(1)-C(2) 1724(4)

C(2)-N(4) 1310(5)

C(2)-S(3) 1724(3)

N(4)-C(15) 1475(5)

N(4)-C(5) 1483(5)

C(5)-C(6) 1505(6)

C(6)-C(7) 1489(7)

C(7)-Si(8) 1873(5)

Si(8)-O(11) 1496(7)

Si(8)-O(13) 1557(11)

Si(8)-O(9) 1565(12)

Si(8)-O(9) 1624(6)

Si(8)-O(13) 1633(5)

S(3)-C(2)-S(1) 11213(19)

C(2)-S(3)-Pd(1) 8590(12)

C(2)-N(4)-C(15) 1217(3)

C(2)-N(4)-C(5) 1206(3)

C(15)-N(4)-C(5) 1177(3)

N(4)-C(5)-C(6) 1148(4)

C(7)-C(6)-C(5) 1142(4)

C(6)-C(7)-Si(8) 1144(3)

O(13)-Si(8)-O(9) 1104(10)

O(11)-Si(8)-O(9) 1059(5)

O(11)-Si(8)-O(13) 1110(3)

O(9)-Si(8)-O(13) 1031(4)

O(13)-Si(8)-O(11) 1029(7)

O(9)-Si(8)-O(11) 1063(8)

O(11)-Si(8)-C(7) 1136(3)

O(13)-Si(8)-C(7) 1206(7)

O(9)-Si(8)-C(7) 1088(12)

O(9)-Si(8)-C(7) 1139(6)

O(13)-Si(8)-C(7) 1089(3)

O(11)-Si(8)-C(7) 1069(7)

C(10)-O(9)-Si(8) 1278(8)

C(12)-O(11)-Si(8) 1307(7)

C(14)-O(13)-Si(8) 1264(7)

231

Si(8)-O(11) 1664(11)

O(9)-C(10) 1395(9)

O(11)-C(12) 1457(8)

O(13)-C(14) 1401(9)

O(9)-C(10) 1410(13)

O(11)-C(12) 1438(14)

O(13)-C(14) 1399(14)

C(15)-C(16) 1517(5)

C(16)-C(17) 1540(6)

C(17)-Si(18) 1853(5)

Si(18)-O(19) 1609(4)

Si(18)-O(21) 1614(4)

Si(18)-O(23) 1620(13)

Si(18)-O(23) 1636(5)

Si(18)-O(19) 1649(13)

Si(18)-O(21) 1658(14)

O(19)-C(20) 1413(8)

O(21)-C(22) 1370(9)

O(23)-C(24) 1359(9)

O(19)-C(20) 1398(16)

O(21)-C(22) 1396(17)

O(23)-C(24) 1392(16)

C(25)-C(26) 1393(5)

C(25)-C(30) 1399(5)

C(26)-C(27) 1388(6)

C(27)-C(28) 1372(7)

C(28)-C(29) 1376(7)

C(29)-C(30) 1395(6)

C(31)-C(32) 1388(5)

C(31)-C(36) 1397(5)

C(32)-C(33) 1389(5)

C(33)-C(34) 1383(6)

C(34)-C(35) 1391(5)

C(35)-C(36) 1383(5)

C(37)-C(38) 1395(5)

C(37)-C(42) 1397(5)

C(38)-C(39) 1382(5)

C(39)-C(40) 1393(6)

C(40)-C(41) 1380(6)

C(41)-C(42) 1383(5)

C(43)-C(44) 1387(5)

C(43)-C(48) 1399(5)

C(44)-C(45) 1393(5)

C(45)-C(46) 1383(6)

C(46)-C(47) 1383(6)

C(47)-C(48) 1389(5)

C(49)-C(50) 1384(5)

C(49)-C(54) 1404(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1377(7)

C(52)-C(53) 1384(7)

C(53)-C(54) 1394(5)

C(55)-C(60) 1391(5)

C(55)-C(56) 1394(5)

C(56)-C(57) 1384(6)

C(57)-C(58) 1386(7)

C(58)-C(59) 1382(7)

C(59)-C(60) 1392(6)

P(3)-F(6) 1588(3)

P(3)-F(5) 1590(3)

P(3)-F(3) 1591(3)

C(10)-O(9)-Si(8) 1321(16)

C(12)-O(11)-Si(8) 1203(13)

C(14)-O(13)-Si(8) 1323(16)

N(4)-C(15)-C(16) 1126(3)

C(15)-C(16)-C(17) 1103(3)

C(16)-C(17)-Si(18) 1159(3)

O(19)-Si(18)-O(21) 1125(4)

O(19)-Si(18)-O(23) 1106(3)

O(21)-Si(18)-O(23) 1077(3)

O(23)-Si(18)-O(19) 1101(10)

O(23)-Si(18)-O(21) 1067(11)

O(19)-Si(18)-O(21) 1059(10)

O(19)-Si(18)-C(17) 1084(2)

O(21)-Si(18)-C(17) 1107(4)

O(23)-Si(18)-C(17) 1215(11)

O(23)-Si(18)-C(17) 1068(3)

O(19)-Si(18)-C(17) 1003(9)

O(21)-Si(18)-C(17) 1112(16)

C(20)-O(19)-Si(18) 1270(6)

C(22)-O(21)-Si(18) 1283(6)

C(24)-O(23)-Si(18) 1306(7)

C(20)-O(19)-Si(18) 1250(17)

C(22)-O(21)-Si(18) 1231(18)

C(24)-O(23)-Si(18) 1266(19)

C(26)-C(25)-C(30) 1189(4)

C(26)-C(25)-P(1) 1195(3)

C(30)-C(25)-P(1) 1215(3)

C(27)-C(26)-C(25) 1204(4)

C(28)-C(27)-C(26) 1209(4)

C(27)-C(28)-C(29) 1191(4)

C(28)-C(29)-C(30) 1215(4)

C(29)-C(30)-C(25) 1192(4)

C(32)-C(31)-C(36) 1202(3)

C(32)-C(31)-P(1) 1202(3)

C(36)-C(31)-P(1) 1195(3)

C(31)-C(32)-C(33) 1193(3)

C(34)-C(33)-C(32) 1206(3)

C(33)-C(34)-C(35) 1201(3)

C(36)-C(35)-C(34) 1198(3)

C(35)-C(36)-C(31) 1201(3)

C(38)-C(37)-C(42) 1186(3)

C(38)-C(37)-P(1) 1181(3)

C(42)-C(37)-P(1) 1233(3)

C(39)-C(38)-C(37) 1207(3)

C(38)-C(39)-C(40) 1204(4)

C(41)-C(40)-C(39) 1189(4)

C(40)-C(41)-C(42) 1212(4)

C(41)-C(42)-C(37) 1201(4)

C(44)-C(43)-C(48) 1197(3)

C(44)-C(43)-P(2) 1250(3)

C(48)-C(43)-P(2) 1153(3)

C(43)-C(44)-C(45) 1194(4)

C(46)-C(45)-C(44) 1208(4)

C(45)-C(46)-C(47) 1200(4)

C(46)-C(47)-C(48) 1198(4)

C(47)-C(48)-C(43) 1203(4)

C(50)-C(49)-C(54) 1194(3)

C(50)-C(49)-P(2) 1226(3)

C(54)-C(49)-P(2) 1179(3)

C(49)-C(50)-C(51) 1203(4)

C(52)-C(51)-C(50) 1201(4)

232

P(3)-F(4) 1591(3)

P(3)-F(1) 1591(3)

P(3)-F(2) 1606(3)

P(2)-Pd(1)-P(1) 9913(3)

P(2)-Pd(1)-S(1) 9341(3)

P(1)-Pd(1)-S(1) 16715(3)

P(2)-Pd(1)-S(3) 16839(3)

P(1)-Pd(1)-S(3) 9221(3)

S(1)-Pd(1)-S(3) 7514(3)

C(37)-P(1)-C(31) 10350(15)

C(37)-P(1)-C(25) 10696(16)

C(31)-P(1)-C(25) 10397(16)

C(37)-P(1)-Pd(1) 12280(11)

C(31)-P(1)-Pd(1) 11250(11)

C(25)-P(1)-Pd(1) 10556(11)

C(43)-P(2)-C(55) 11078(16)

C(43)-P(2)-C(49) 10469(16)

C(55)-P(2)-C(49) 10265(16)

C(43)-P(2)-Pd(1) 10997(12)

C(55)-P(2)-Pd(1) 11546(12)

C(49)-P(2)-Pd(1) 11259(11)

C(2)-S(1)-Pd(1) 8681(12)

N(4)-C(2)-S(3) 1239(3)

N(4)-C(2)-S(1) 1239(3)

C(51)-C(52)-C(53) 1203(4)

C(52)-C(53)-C(54) 1200(4)

C(53)-C(54)-C(49) 1198(4)

C(60)-C(55)-C(56) 1195(3)

C(60)-C(55)-P(2) 1194(3)

C(56)-C(55)-P(2) 1210(3)

C(57)-C(56)-C(55) 1198(4)

C(56)-C(57)-C(58) 1207(4)

C(59)-C(58)-C(57) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(55)-C(60)-C(59) 1202(4)

F(6)-P(3)-F(5) 8938(18)

F(6)-P(3)-F(3) 9022(16)

F(5)-P(3)-F(3) 1796(2)

F(6)-P(3)-F(4) 9002(16)

F(5)-P(3)-F(4) 9024(18)

F(3)-P(3)-F(4) 8977(16)

F(6)-P(3)-F(1) 17916(19)

F(5)-P(3)-F(1) 913(2)

F(3)-P(3)-F(1) 8906(18)

F(4)-P(3)-F(1) 904(2)

F(6)-P(3)-F(2) 8873(16)

F(5)-P(3)-F(2) 9101(19)

F(3)-P(3)-F(2) 8896(16)

F(4)-P(3)-F(2) 1782(2)

F(1)-P(3)-F(2) 908(2)

233

Appendix B Calculation of palladium loading in 36SiO2Fe3O4

Appendix C Calculation of 3 mol of palladium loading (36SiO2Fe3O4 as

example)

ii

Declaration

I declare that the work described in this thesis was carried out in accordance with the

regulations of Imperial College London The work is my own except where indicated

in the text and no part of the thesis was submitted previously for a degree at this or

any other university

iii




















iv

Publications








v

Acknowledgements













they are missing








vi












vii

Abstract




























viii










ix

Abbreviations






x

Contents

Declaration ii


Publication iv

Acknowledgement v

Abstract vii

Abbreviations ix

Contents x



1





6












xi

16 References 31






45


51







25 Conclusion 66

26 References 67





73


73



79



xii



84


87




90


35 Conclusion 96

36 References 98





102





112



118




121

45 Conclusion 128

46 References 130

xiii





133




136


(37) 138









148


149


152

55 Conclusion 154

56 References 156


61 Conclusions 158

62 Future work 159

xiv





731 KS2CN(CH2py)2 (1) 163

732 [Au(S2CN(CH2py)2)(PPh3)] (2) 163

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3) 164





738 [Ni(S2C-N(CH2py)2)] (8) 166







170


170


7317 (SC6H4CO2H-4)2 (17) 172

7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18) 172



173


174

xv






741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 178

742 [Pd(S2CNEt2)2] (24) 178



(26) 179

745 [Pd(Me2dazdt)2]I6 (27) 180

746 [PdI2(Me2dazdt)] (28) 180

747 [Pd(Cy2DTO)2]I8 (29) 180



751 (TBA)2[Pd2I6] (30) 186

752 Trans-PdI2(PPh3)2 (31) 186

753 [PdI2(dppe)] (32) 187

754 [PdI2(dppf)] (33) 187







xvi




195


195


196


8 Appendices



201



204



(22)

208



212



216


219



223



223


229



1

























2











(Figure 112)8




3




















4
























5













6














7




















8























9












catalysis









10






























carbon (C-C) bond

11















C)42


12





















metals


13









mechanisms















14



















15

















16














(80)56











17


















18


















19



























20


























21




















22














23












of product92







24
















25






















0

500

1000

1500

2000

2500

1992 1997 2003 2008 2014

Pri

ce (

USD

pe

r O

z)

Year

Pt

Pd

26





















27



























PGMs112






28



concerns114


















143

29


15 Thesis overview










also investigated



30











31

16 References
























32

37 2466ndash2468

























33























70 Chem Abs 1969 71 114951




34
























35























36


37

























(Figure 211)


38
















manner













39
















mz 200











40




at mz 274


41


































42


































43














44

































45




ligand










Figure 231












46













47






















formulation










48

















complexes
















49















50
































51





nitrogen)

























52


















53





























54




















55


































56




















8764(18)deg]37


57































58


















59
















(Figure 245)








60










NP1 (Figure 246)








61




















0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

(

)

Temperature ()

62


















63







0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

64



















65



0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

66

25 Conclusion















67

26 References





















68























69









70































71

























72

















catalystsrdquo19












73































74
















75






















76









77











Pt(PPh3)2

27

2354(1) 2355(1)

1318 (6)

1723(5) 1725(5)

1118(3)

7467 (4)

Pd(dppf)27

23370(1) 2358(1)

1322(6)

1725(5) 1735(5)

1121(3)

7518(5)

Pd(PPh3)2 (25-A)

23304(10) 23536(10)

1302(5)

1722(4) 1735(4)

1112(2)

7504(4)

Pd(PPh3)2 (25-B)

23388 (8) 23479(9)

1326(4)

1714(4) 1727(4)

11276(19)

7536(3)





(Figure 324)

78












Pd(dppf)26

23348(6) 23516(6) 23347(6) 23445(7)

1313(3) 1323(3)

1728(2) 1719(2) 1709(2) 1723(2)

11188(14) 11215(13)

7507(2) 7498(2)

Pd(PPh3)2 (26)

23720(16) 23190(15) 23735(17) 23180(15

1323(8) 1316(9)

1715(7) 1718(6) 1722(7) 1727(7)

1132(4) 1119(4)

7528(5) 7505(5)

79























80
















81















A

Me MeOH 12 22 95

Et EtOH 51 24 80



B Me MeOH 19 18 80

82



reaction























block and vials





83



























byproducts

84








impact


(SOCDTC)







86

75

8784

87

69

8784

0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Perc

enta

ge y

ield

(

)


22hr 2hr

85


time


















30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Pd loading (mol)

86



















0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Yie

ld

)

Catalyst


87































88










(h)

Yield

()

SD

A

Et

23 2 89 (20)

24 2 83 (10)

25 2 64 (21)

26 2 65 (35)

Pri

23 8 90 (14)

24 24 99 (00)

25 4 97 (12)

26 8 91 (25)

CH2CF3

23 4 92 (10)

24 4 99 (00)

25 2 99 (06)

26 2 95 (17)

B

Me

23 2 66 (02)

24 6 40 (02)

25 2 78 (02)

26 2 46 (44)






89





























90



(mol)

Temperature

(degC)

Time

(h)

Yield

()

A

Me

Me

27 1 100

100

2 87

Pd(OAc)2 1 22 95

Me 27 1 50 2 67

Me Pd(OAc)2 1 50 2 33


catalysts (SOCDTO)










0

20

40

60

80

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

1 mol 2 mol

91


















0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Time (hours)

1 mol 2 mol

92



(mol)

Time

(h)

Yield

()

SD

()

1

1 39 05

A

Pri

27

2 48 06

3 52 07

4 52 09

5 53 08

Pri

27

2

1 74 31

2 79 23

3 81 27

4 83 27

5 83 30

A

CF3CH2

27

2

1 49 05

2 72 09

3 85 11

4 92 00

5 96 05






or 2 hours

93


T = 50 degC








89

9899 99

85

92

9596

75

80

85

90

95

100

105

1 2 3 4

Yie

ld (

)

Time (hours)


40

50

60

70

80

90

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

EtOH iPrOH

94













0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10

Yie

ld (

)

Time (hours)


95







(mol)

Time

(h)

Yield

()

SD

()

2

1 53 11

B

OMe

28

2 95 05

3 100 05

4 100 00

5 100 00

B

OMe

29

2

1 54 20

2 89 08

3 99 02

4 100 00

5 100 00











96




method (100)

35 Conclusion



























97









98

36 References




















99











100






























101













and Singulair56

















102






















secondary source







103
















104























105













above11













sections






106

























107









A

1 mol

Me 2 94 ( 02)

Et 2 43 ( 02)

Pri 2 52 ( 47)

CH2CF3 2 93 ( 30)

2 mol

Me 2 99 ( 04)

EtOH 2 81 ( 33)

Pri 2 75 ( 40)

CH2CF3 2 99 ( 15)













108






















original work

109













50

MeOH

11 Pd

1 34

2 39

5 73

22 87

100

MeOH

11 Pd

1 91

2 90

5 92

22 92







A MeOH 11 22 95

110




















111








nm17

















112






catalyst
















113








0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25

Yiel

d (

)

Time (hours)


114

















0

20

40

60

80

100

120

0 5 10 15 20 25 30

Yiel

d (

)

Time (hours)


115













B Me 1 mol 2 80 (02)

2 mol 2 87 (16)







116





















B

MeOH

1 mol

2 96 ( 02)

4 94 ( 17)

6 96 ( 03)

24 95 (12)

B

MeOH

2 mol

2 99 (06)

4 99 (04)

6 99 (04)

24 99 (05)



117







C AcOH 1 mol 2 61 ( 30)

2 mol 2 83 ( 40)













C

AcOH

1 mol

2 44 ( 28)

4 55 ( 06)

6 62 ( 25)

24 71 ( 16)

C

AcOH

2 mol

2 71 ( 78)

4 71 ( 21)

6 72 ( 13)

24 85 ( 38)

118


















119




























120









coupling reaction



















reading

121













coupling reactions












122


Catalyst Pd

loadings

(mol )

Yield ()


[PdI2(PPh3)2] (31)

05



























123

















coupling reactions




80

85

90

95

100

105


Yiel

d (

)

Catalysts

30 min 60 min

124















K2CO3 in ethanol











125




















80

85

90

95

100

30 60 90

Yie

ld (

)

Time (min)

(TBA)₂[Pd₂I₆] (30) [PdCl₂(PPh₃)₂]

126

















0

10

20

30

40

50

60

70

80

90

100

90 120 150

Pro

du

ct y

ield

(

)

Time (min)


127




60 968 plusmn 04


60 973 plusmn 15


60 996 plusmn 01


60 995 plusmn 01









0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


128










45 Conclusion











0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


129




excellent yield










130

46 References























131
























132
































133














oxidant PhI(OAc)2











134






















135
















products










both complexes







136
















137












138



25-A

23304(10)

23536(10)

1302(5)

1722(4)

1735(4)

1112(2)

7504(4)

36-A

23294(9)

23458(9)

1306(4)

1726(3)

1717(4)

1114(2)

7492(3)

36-B

23293(9)

23476(10)

1312(5)

1719(4)

1722(4)

1111(2)

7472(3)








C(10)-O(9)-Si(8) 1226˚ (5) 1228˚ (7) 02˚

C(12)-O(11)-Si(8) 1220˚ (5) 1249˚ (6) 29˚

C(14)-O(13)-Si(8) 1221˚ (6) 1273˚ (7) 52˚







139











140













Reaction

Catalyst Pd

(mol)

Temperature

(degC)

Time

(h)

Yield

()

SD

A

36

1

100

2

85 ( 06)

37 85 ( 07)

23 87 (10)

141











product








0

10

20

30

40

50

60

70

1 2 3 4 5 6

Yiel

d (

)

Time (hours)

36 37

142



















0

20

40

60

80

100

120

0 1 2 3 4 5 6

Yiel

d (

)


36 37

143









(h)

Yield

()

SD

Et

23 2 89 (20)

A

36 24 99 (04)

37 24 42 (34)

CH2CF3

23 4 92 (10)

36 6 98 (02)

37 6 90 (17)

B Me 23 2 66 (02)

37 6 60 (38)















144





magnetic field14















145






















146



nanoparticles















147



















ethanol and dried









148







and dried















149








complexes













physisorbed

150











nanoparticles


151






















60

65

70

75

80

85

90

95

100

0 100 200 300 400 500 600

Weig

ht (

)

Temperature ()


152



palladium catalyst










h)








153



36SiO2Fe3O4 32 13 5 -

36SiO2Fe3O4 32 27 10 6



























154









55 Conclusion






















155






156

56 References























157










158


61 Conclusions



















donor groups










159

















system

62 Future work













160



161

7 Experimental





























162


























163


731 KS2CN(CH2py)2 (1)








mg (84) IR 2923 (νC-H) 2361 1591 1570 1474 1434 (νC-N) 1358 1302 1183





(100) [M-K]ˉ

732 [Au(S2CN(CH2py)2)(PPh3)] (2)












N 56

164

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3)














37 Found C 497 H 37 N 35















C 585 H 44 N 34

165




















677 H 48 N 41











166









45 N 35











1915 (νCO) 1589 1570 1475 1432 1409 1207 1157 1090 1001 750 689 cmndash1





37 Found C 699 H 47 N 37

738 [Ni(S2C-N(CH2py)2)] (8)




167









H 40 N 138 Found C 433 H 36 N 108




















199616) C 641 H 45 N 14 Found C 637 H 42 N 18

168



















H 43 N 16













169







H 42 N 10












715 H 51 N 10











170











(CO) 1890 (CO) 1531 (OCO) 1481 1433 1391 1184 1090 979 827 743 692 cmndash












= 208951) C 615 H 41 N 13 Found C 614 H 39 N 14








171








226170) C 643 H 39 N 12 Found C 641 H 38 N 12



















C 509 H 33 N 13

172

7317 (SC6H4CO2H-4)2 (17)






2669 2552 1676 (VCO) 1591 1423 1323 1292 1181 1116 933 850 cmndash1 1H NMR



7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18)





















H 42 Found C 586 H 42

173































174









= 138224) C 617 H 42 Found C 617 H 41


















175






1535 1481 1434 1419 1176 1095 862 744 692 cm-1 1H NMR (CD2Cl2) 578 (d







H 33 N 16 Found C 526 H 34 N 17



















176














x 2 2 x 2H PCH2P) 661 (m 4H C6H5) 710 726 738 754 772 794 (m x 6 36H


















177





178


741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 925













742 [Pd(S2CNEt2)2] (24)26













179






(79) IR (ATR) 1514 1480 1434 1280 1239 1094 999 (νC-S) 831 (νPF) cm-1 1H






524 H 38 N 16 Found C 525 H 37 N 16




















180


745 [Pd(Me2dazdt)2]I6 (27)







1429 1393 1357 1330 1287 1283 1107 1073 1028 981 825 743610 581 532


NCH2 JHH = 67 Hz)









1527 1460 1423 1395 1359 1330 1286 1264 1223 1114 1073 1027 958 897



literature28

747 [Pd(Cy2DTO)2]I8 (29)





181







199 H 29 N 33 Found C 203 H 28 N 34
















data

182





183

























184












method data (99)





Hz 20 Hz) 726 (dd 1H J = 80 Hz 10 Hz) 419 (s3H)





3H J = 70 Hz)




60 Hz) 150 (t 6H J = 60 Hz)



185






3H)

186


751 (TBA)2[Pd2I6]30 (30)


























187

753 [PdI2(dppe)] (32)





Yield 325 mg (87) IR 3052 1437 1100 998 877 811 701 688 678 cm-1 1H




754 [PdI2(dppf)] (33)






= 242 (s dppf) ppm







188












step












189






















190






by 1H NMR




746 (dd 1H JHH = 786 Hz 42 Hz) 586 (s2H) 216 (s 3H)











isolated yield

191



















192



















C 310 H 60 N 45












193






H 66 N 31 Found C 341 H 67 N 32



















47 N 14






194





























195






(129 g)














603 563 (νFeO) cm-1









196

SiO236 NP



SiO236 NP











36SiO2Fe3O4


588 (νFeO) cm-1


37SiO2Fe3O4



197










catalyst system





NMR



198

References




















199






















200

2013 49 11358ndash60

201

Appendices



N(CH2py)2)(CO)(PPh3)2] (5)









b = 148523(7) Aring = 82606(3)deg

c = 179728(7) Aring = 87478(3)deg




202

F(000) 1164

















Ru(1)-C(28) 1836(3)

Ru(1)-C(19) 2083(3)

Ru(1)-P(2) 23706(8)

Ru(1)-P(1) 23823(8)

Ru(1)-S(3) 24740(8)

Ru(1)-S(1) 25025(8)

P(1)-C(29) 1834(3)

P(1)-C(35) 1834(3)

P(1)-C(41) 1845(4)

P(2)-C(53) 1827(3)

P(2)-C(59) 1837(3)

P(2)-C(47) 1845(3)

S(1)-C(2) 1715(3)

C(2)-N(4) 1333(4)

C(2)-S(3) 1698(3)

N(4)-C(5) 1457(5)

N(4)-C(12) 1461(4)

C(5)-C(6) 1516(5)

C(6)-N(7) 1344(5)

C(6)-C(11) 1372(5)

N(7)-C(8) 1353(6)

C(8)-C(9) 1382(7)

C(9)-C(10) 1366(7)

C(10)-C(11) 1368(6)

C(12)-C(13) 1519(6)

C(13)-N(14) 1335(5)

C(13)-C(18) 1370(6)

N(14)-C(15) 1360(7)

C(15)-C(16) 1339(9)

C(16)-C(17) 1354(8)

C(17)-C(18) 1398(7)

C(29)-P(1)-Ru(1) 11804(10)

C(35)-P(1)-Ru(1) 11715(11)

C(41)-P(1)-Ru(1) 11341(12)

C(53)-P(2)-C(59) 10292(15)

C(53)-P(2)-C(47) 10443(14)

C(59)-P(2)-C(47) 9991(14)

C(53)-P(2)-Ru(1) 11295(10)

C(59)-P(2)-Ru(1) 11877(11)

C(47)-P(2)-Ru(1) 11586(11)

C(2)-S(1)-Ru(1) 8783(12)

N(4)-C(2)-S(3) 1241(3)

N(4)-C(2)-S(1) 1227(3)

S(3)-C(2)-S(1) 11319(18)

C(2)-S(3)-Ru(1) 8915(11)

C(2)-N(4)-C(5) 1221(3)

C(2)-N(4)-C(12) 1210(3)

C(5)-N(4)-C(12) 1168(3)

N(4)-C(5)-C(6) 1153(3)

N(7)-C(6)-C(11) 1231(4)

N(7)-C(6)-C(5) 1139(3)

C(11)-C(6)-C(5) 1230(3)

C(6)-N(7)-C(8) 1168(4)

N(7)-C(8)-C(9) 1230(4)

C(10)-C(9)-C(8) 1182(4)

C(9)-C(10)-C(11) 1201(4)

C(10)-C(11)-C(6) 1187(4)

N(4)-C(12)-C(13) 1144(3)

N(14)-C(13)-C(18) 1227(4)

N(14)-C(13)-C(12) 1133(4)

C(18)-C(13)-C(12) 1240(3)

C(13)-N(14)-C(15) 1159(5)

203

C(19)-C(20) 1333(5)

C(20)-C(21) 1477(5)

C(21)-C(22) 1395(5)

C(21)-C(26) 1403(5)

C(22)-C(23) 1388(5)

C(23)-C(24) 1386(6)

C(24)-C(25) 1384(6)

C(24)-C(27) 1519(6)

C(25)-C(26) 1386(5)

C(28)-O(28) 1138(4)

C(29)-C(34) 1388(5)

C(29)-C(30) 1397(5)

C(30)-C(31) 1383(5)

C(31)-C(32) 1387(6)

C(32)-C(33) 1378(6)

C(33)-C(34) 1396(5)

C(35)-C(36) 1373(6)

C(35)-C(40) 1393(5)

C(36)-C(37) 1382(5)

C(37)-C(38) 1380(6)

C(38)-C(39) 1359(7)

C(39)-C(40) 1404(5)

C(41)-C(42) 1383(6)

C(41)-C(46) 1393(5)

C(42)-C(43) 1389(7)

C(43)-C(44) 1372(9)

C(44)-C(45) 1371(8)

C(45)-C(46) 1392(6)

C(47)-C(52) 1386(4)

C(47)-C(48) 1393(5)

C(48)-C(49) 1384(5)

C(49)-C(50) 1384(5)

C(50)-C(51) 1381(6)

C(51)-C(52) 1396(5)

C(53)-C(58) 1388(5)

C(53)-C(54) 1393(5)

C(54)-C(55) 1407(5)

C(55)-C(56) 1375(6)

C(56)-C(57) 1384(6)

C(57)-C(58) 1393(5)

C(59)-C(64) 1384(5)

C(59)-C(60) 1395(5)

C(60)-C(61) 1394(5)

C(61)-C(62) 1381(7)

C(62)-C(63) 1378(7)

C(63)-C(64) 1399(5)

C(28)-Ru(1)-C(19) 9900(14)

C(28)-Ru(1)-P(2) 9001(10)

C(19)-Ru(1)-P(2) 8442(9)

C(28)-Ru(1)-P(1) 8661(11)

C(19)-Ru(1)-P(1) 8546(9)

P(2)-Ru(1)-P(1) 16869(3)

C(28)-Ru(1)-S(3) 16962(11)

C(19)-Ru(1)-S(3) 9137(9)

P(2)-Ru(1)-S(3) 9142(3)

P(1)-Ru(1)-S(3) 9385(3)

C(28)-Ru(1)-S(1) 9981(11)

C(19)-Ru(1)-S(1) 16110(9)

P(2)-Ru(1)-S(1) 9381(3)

P(1)-Ru(1)-S(1) 9739(3)

C(16)-C(15)-N(14) 1249(5)

C(15)-C(16)-C(17) 1188(5)

C(16)-C(17)-C(18) 1187(5)

C(13)-C(18)-C(17) 1190(4)

C(20)-C(19)-Ru(1) 1263(2)

C(19)-C(20)-C(21) 1261(3)

C(22)-C(21)-C(26) 1174(3)

C(22)-C(21)-C(20) 1231(3)

C(26)-C(21)-C(20) 1195(3)

C(23)-C(22)-C(21) 1211(3)

C(24)-C(23)-C(22) 1212(4)

C(25)-C(24)-C(23) 1181(4)

C(25)-C(24)-C(27) 1218(4)

C(23)-C(24)-C(27) 1202(4)

C(24)-C(25)-C(26) 1213(3)

C(25)-C(26)-C(21) 1210(3)

O(28)-C(28)-Ru(1) 1776(3)

C(34)-C(29)-C(30) 1192(3)

C(34)-C(29)-P(1) 1224(3)

C(30)-C(29)-P(1) 1183(3)

C(31)-C(30)-C(29) 1202(3)

C(30)-C(31)-C(32) 1204(3)

C(33)-C(32)-C(31) 1196(3)

C(32)-C(33)-C(34) 1204(4)

C(29)-C(34)-C(33) 1201(3)

C(36)-C(35)-C(40) 1179(3)

C(36)-C(35)-P(1) 1208(3)

C(40)-C(35)-P(1) 1214(3)

C(35)-C(36)-C(37) 1214(4)

C(38)-C(37)-C(36) 1208(5)

C(39)-C(38)-C(37) 1187(4)

C(38)-C(39)-C(40) 1210(4)

C(35)-C(40)-C(39) 1202(4)

C(42)-C(41)-C(46) 1184(4)

C(42)-C(41)-P(1) 1223(3)

C(46)-C(41)-P(1) 1193(3)

C(41)-C(42)-C(43) 1208(5)

C(44)-C(43)-C(42) 1201(5)

C(45)-C(44)-C(43) 1201(4)

C(44)-C(45)-C(46) 1201(4)

C(45)-C(46)-C(41) 1205(4)

C(52)-C(47)-C(48) 1186(3)

C(52)-C(47)-P(2) 1223(3)

C(48)-C(47)-P(2) 1189(2)

C(49)-C(48)-C(47) 1207(3)

C(50)-C(49)-C(48) 1203(4)

C(51)-C(50)-C(49) 1196(3)

C(50)-C(51)-C(52) 1200(3)

C(47)-C(52)-C(51) 1207(3)

C(58)-C(53)-C(54) 1197(3)

C(58)-C(53)-P(2) 1197(2)

C(54)-C(53)-P(2) 1199(3)

C(53)-C(54)-C(55) 1196(3)

C(56)-C(55)-C(54) 1201(3)

C(55)-C(56)-C(57) 1204(3)

C(56)-C(57)-C(58) 1200(4)

C(53)-C(58)-C(57) 1203(3)

C(64)-C(59)-C(60) 1194(3)

C(64)-C(59)-P(2) 1210(3)

C(60)-C(59)-P(2) 1196(3)

C(61)-C(60)-C(59) 1201(4)

204

S(3)-Ru(1)-S(1) 6983(3)

C(29)-P(1)-C(35) 10221(15)

C(29)-P(1)-C(41) 10252(17)

C(35)-P(1)-C(41) 10111(16)

C(62)-C(61)-C(60) 1199(4)

C(63)-C(62)-C(61) 1205(4)

C(62)-C(63)-C(64) 1198(4)

C(59)-C(64)-C(63) 1204(4)





5(C H2 Cl2)






b = 217537(9) Aring = 92572(4)deg

c = 304002(14) Aring = 90deg

205




F(000) 3136

















Ru(1)-O(3) 2161(4)

Ru(1)-O(1) 2232(4)

Ru(1)-P(43) 22640(16)

Ru(1)-P(13) 22916(17)

Ru(1)-P(11) 23361(16)

Ru(1)-P(41) 23570(16)

Ru(1)-C(2) 2531(6)

O(1)-C(2) 1267(7)

C(2)-O(3) 1260(7)

C(2)-C(4) 1489(8)

C(4)-C(9) 1370(9)

C(4)-C(5) 1380(8)

C(5)-C(6) 1387(8)

C(6)-N(7) 1333(8)

C(6)-C(6)1 1475(12)

N(7)-C(8) 1338(9)

C(8)-C(9) 1390(9)

P(11)-C(20) 1806(6)

P(11)-C(14) 1818(6)

P(11)-C(12) 1829(6)

C(12)-P(13) 1854(6)

P(13)-C(26) 1815(6)

P(13)-C(32) 1820(6)

C(14)-C(15) 1371(9)

C(14)-C(19) 1395(8)

C(15)-C(16) 1395(9)

C(16)-C(17) 1373(10)

C(5)-C(6)-C(6)1 1212(7)

C(6)-N(7)-C(8) 1175(6)

N(7)-C(8)-C(9) 1236(6)

C(4)-C(9)-C(8) 1180(6)

C(20)-P(11)-C(14) 1050(3)

C(20)-P(11)-C(12) 1088(3)

C(14)-P(11)-C(12) 1074(3)

C(20)-P(11)-Ru(1) 1157(2)

C(14)-P(11)-Ru(1) 1235(2)

C(12)-P(11)-Ru(1) 950(2)

P(11)-C(12)-P(13) 948(3)

C(26)-P(13)-C(32) 1043(3)

C(26)-P(13)-C(12) 1024(3)

C(32)-P(13)-C(12) 1072(3)

C(26)-P(13)-Ru(1) 1188(2)

C(32)-P(13)-Ru(1) 1249(2)

C(12)-P(13)-Ru(1) 958(2)

C(15)-C(14)-C(19) 1200(6)

C(15)-C(14)-P(11) 1205(5)

C(19)-C(14)-P(11) 1194(5)

C(14)-C(15)-C(16) 1200(6)

C(17)-C(16)-C(15) 1194(7)

C(18)-C(17)-C(16) 1208(7)

C(17)-C(18)-C(19) 1202(7)

C(18)-C(19)-C(14) 1195(7)

C(25)-C(20)-C(21) 1195(6)

C(25)-C(20)-P(11) 1227(5)

206

C(17)-C(18) 1370(11)

C(18)-C(19) 1377(9)

C(20)-C(25) 1371(9)

C(20)-C(21) 1395(9)

C(21)-C(22) 1370(10)

C(22)-C(23) 1375(12)

C(23)-C(24) 1383(13)

C(24)-C(25) 1397(11)

C(26)-C(31) 1375(9)

C(26)-C(27) 1402(8)

C(27)-C(28) 1383(9)

C(28)-C(29) 1361(10)

C(29)-C(30) 1388(10)

C(30)-C(31) 1384(10)

C(32)-C(37) 1378(9)

C(32)-C(33) 1412(9)

C(33)-C(34) 1376(10)

C(34)-C(35) 1354(11)

C(35)-C(36) 1381(11)

C(36)-C(37) 1385(9)

P(41)-C(50) 1818(6)

P(41)-C(44) 1823(7)

P(41)-C(42) 1851(6)

C(42)-P(43) 1849(6)

P(43)-C(62) 1811(6)

P(43)-C(56) 1829(7)

C(44)-C(49) 1384(9)

C(44)-C(45) 1387(9)

C(45)-C(46) 1383(10)

C(46)-C(47) 1377(12)

C(47)-C(48) 1386(12)

C(48)-C(49) 1366(11)

C(50)-C(55) 1375(9)

C(50)-C(51) 1398(9)

C(51)-C(52) 1386(9)

C(52)-C(53) 1364(11)

C(53)-C(54) 1385(11)

C(54)-C(55) 1382(10)

C(56)-C(57) 1357(9)

C(56)-C(61) 1388(9)

C(57)-C(58) 1392(10)

C(58)-C(59) 1376(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1380(10)

C(62)-C(63) 1386(9)

C(62)-C(67) 1395(8)

C(63)-C(64) 1396(9)

C(64)-C(65) 1362(10)

C(65)-C(66) 1370(10)

C(66)-C(67) 1385(8)

B(70)-C(83) 1628(11)

B(70)-C(77) 1635(11)

B(70)-C(89) 1644(11)

B(70)-C(71) 1659(10)

C(71)-C(76) 1367(10)

C(71)-C(72) 1398(10)

C(72)-C(73) 1367(11)

C(73)-C(74) 1346(13)

C(74)-C(75) 1370(13)

C(75)-C(76) 1403(11)

C(77)-C(82) 1376(10)

C(21)-C(20)-P(11) 1172(5)

C(22)-C(21)-C(20) 1209(7)

C(21)-C(22)-C(23) 1193(8)

C(22)-C(23)-C(24) 1211(8)

C(23)-C(24)-C(25) 1191(8)

C(20)-C(25)-C(24) 1201(7)

C(31)-C(26)-C(27) 1182(6)

C(31)-C(26)-P(13) 1203(5)

C(27)-C(26)-P(13) 1207(5)

C(28)-C(27)-C(26) 1201(6)

C(29)-C(28)-C(27) 1208(6)

C(28)-C(29)-C(30) 1201(7)

C(31)-C(30)-C(29) 1192(7)

C(26)-C(31)-C(30) 1217(7)

C(37)-C(32)-C(33) 1184(6)

C(37)-C(32)-P(13) 1193(5)

C(33)-C(32)-P(13) 1221(5)

C(34)-C(33)-C(32) 1195(7)

C(35)-C(34)-C(33) 1215(7)

C(34)-C(35)-C(36) 1199(7)

C(35)-C(36)-C(37) 1199(8)

C(32)-C(37)-C(36) 1208(7)

C(50)-P(41)-C(44) 1009(3)

C(50)-P(41)-C(42) 1075(3)

C(44)-P(41)-C(42) 1055(3)

C(50)-P(41)-Ru(1) 1224(2)

C(44)-P(41)-Ru(1) 1243(2)

C(42)-P(41)-Ru(1) 9385(19)

P(43)-C(42)-P(41) 952(3)

C(62)-P(43)-C(56) 1029(3)

C(62)-P(43)-C(42) 1067(3)

C(56)-P(43)-C(42) 1063(3)

C(62)-P(43)-Ru(1) 1294(2)

C(56)-P(43)-Ru(1) 1125(2)

C(42)-P(43)-Ru(1) 970(2)

C(49)-C(44)-C(45) 1201(7)

C(49)-C(44)-P(41) 1214(5)

C(45)-C(44)-P(41) 1185(5)

C(46)-C(45)-C(44) 1188(7)

C(47)-C(46)-C(45) 1211(8)

C(46)-C(47)-C(48) 1195(8)

C(49)-C(48)-C(47) 1200(8)

C(48)-C(49)-C(44) 1206(7)

C(55)-C(50)-C(51) 1187(6)

C(55)-C(50)-P(41) 1226(5)

C(51)-C(50)-P(41) 1185(5)

C(52)-C(51)-C(50) 1195(6)

C(53)-C(52)-C(51) 1208(7)

C(52)-C(53)-C(54) 1203(7)

C(55)-C(54)-C(53) 1188(7)

C(50)-C(55)-C(54) 1218(7)

C(57)-C(56)-C(61) 1194(6)

C(57)-C(56)-P(43) 1190(5)

C(61)-C(56)-P(43) 1214(5)

C(56)-C(57)-C(58) 1204(7)

C(59)-C(58)-C(57) 1206(7)

C(60)-C(59)-C(58) 1184(7)

C(59)-C(60)-C(61) 1214(7)

C(60)-C(61)-C(56) 1197(7)

C(63)-C(62)-C(67) 1188(6)

C(63)-C(62)-P(43) 1211(5)

207

C(77)-C(78) 1406(11)

C(78)-C(79) 1390(11)

C(79)-C(80) 1367(12)

C(80)-C(81) 1350(13)

C(81)-C(82) 1412(12)

C(83)-C(88) 1388(11)

C(83)-C(84) 1410(11)

C(84)-C(85) 1398(12)

C(85)-C(86) 1379(14)

C(86)-C(87) 1372(14)

C(87)-C(88) 1399(12)

C(89)-C(94) 1392(10)

C(89)-C(90) 1412(10)

C(90)-C(91) 1387(11)

C(91)-C(92) 1365(13)

C(92)-C(93) 1353(12)

C(93)-C(94) 1402(11)

C(100)-Cl(2) 1707(11)

C(100)-Cl(1) 1727(11)

C(110)-Cl(4) 1639(14)

C(110)-Cl(3) 1720(12)

C(120)-Cl(5) 1670(15)

C(120)-Cl(6) 1751(16)

O(3)-Ru(1)-O(1) 5979(15)

O(3)-Ru(1)-P(43) 9947(12)

O(1)-Ru(1)-P(43) 15664(11)

O(3)-Ru(1)-P(13) 16018(12)

O(1)-Ru(1)-P(13) 10841(11)

P(43)-Ru(1)-P(13) 9445(6)

O(3)-Ru(1)-P(11) 9159(12)

O(1)-Ru(1)-P(11) 9023(11)

P(43)-Ru(1)-P(11) 10176(6)

P(13)-Ru(1)-P(11) 7170(6)

O(3)-Ru(1)-P(41) 9644(12)

O(1)-Ru(1)-P(41) 9776(11)

P(43)-Ru(1)-P(41) 7245(6)

P(13)-Ru(1)-P(41) 10118(6)

P(11)-Ru(1)-P(41) 17076(6)

O(3)-Ru(1)-C(2) 2985(16)

O(1)-Ru(1)-C(2) 3003(16)

P(43)-Ru(1)-C(2) 12894(14)

P(13)-Ru(1)-C(2) 13584(14)

P(11)-Ru(1)-C(2) 8942(13)

P(41)-Ru(1)-C(2) 9982(13)

C(2)-O(1)-Ru(1) 882(3)

O(3)-C(2)-O(1) 1201(5)

O(3)-C(2)-C(4) 1191(5)

O(1)-C(2)-C(4) 1208(5)

O(3)-C(2)-Ru(1) 586(3)

O(1)-C(2)-Ru(1) 618(3)

C(4)-C(2)-Ru(1) 1735(4)

C(2)-O(3)-Ru(1) 916(4)

C(67)-C(62)-P(43) 1201(5)

C(62)-C(63)-C(64) 1199(6)

C(65)-C(64)-C(63) 1203(7)

C(64)-C(65)-C(66) 1207(6)

C(65)-C(66)-C(67) 1197(6)

C(66)-C(67)-C(62) 1206(6)

C(83)-B(70)-C(77) 1137(6)

C(83)-B(70)-C(89) 1124(6)

C(77)-B(70)-C(89) 1039(6)

C(83)-B(70)-C(71) 1032(6)

C(77)-B(70)-C(71) 1114(6)

C(89)-B(70)-C(71) 1124(6)

C(76)-C(71)-C(72) 1146(7)

C(76)-C(71)-B(70) 1245(7)

C(72)-C(71)-B(70) 1209(7)

C(73)-C(72)-C(71) 1239(8)

C(74)-C(73)-C(72) 1201(9)

C(73)-C(74)-C(75) 1188(8)

C(74)-C(75)-C(76) 1206(9)

C(71)-C(76)-C(75) 1219(8)

C(82)-C(77)-C(78) 1150(7)

C(82)-C(77)-B(70) 1238(7)

C(78)-C(77)-B(70) 1208(7)

C(79)-C(78)-C(77) 1230(8)

C(80)-C(79)-C(78) 1199(9)

C(81)-C(80)-C(79) 1191(9)

C(80)-C(81)-C(82) 1211(8)

C(77)-C(82)-C(81) 1220(8)

C(88)-C(83)-C(84) 1154(8)

C(88)-C(83)-B(70) 1249(8)

C(84)-C(83)-B(70) 1196(8)

C(85)-C(84)-C(83) 1222(10)

C(86)-C(85)-C(84) 1197(10)

C(87)-C(86)-C(85) 1201(10)

C(86)-C(87)-C(88) 1194(11)

C(83)-C(88)-C(87) 1232(10)

C(94)-C(89)-C(90) 1145(7)

C(94)-C(89)-B(70) 1249(6)

C(90)-C(89)-B(70) 1204(7)

C(91)-C(90)-C(89) 1227(8)

C(92)-C(91)-C(90) 1202(8)

C(93)-C(92)-C(91) 1196(9)

C(92)-C(93)-C(94) 1206(8)

C(89)-C(94)-C(93) 1224(8)

Cl(2)-C(100)-Cl(1) 1150(7)

Cl(4)-C(110)-Cl(3) 1199(8)

Cl(5)-C(120)-Cl(6) 1119(9)

208





25(C H2 Cl2)






b = 147789(5) Aring = 73377(3)deg

c = 214417(6) Aring = 75105(3)deg




F(000) 1926







209











Au(1)-P(11) 22545(16)

Au(1)-S(10) 23027(16)

Re(1)-C(83) 1895(7)

Re(1)-C(84) 1915(7)

Re(1)-C(85) 1931(9)

Re(1)-C(85) 1947(7)

Re(1)-N(43) 2161(5)

Re(1)-N(32) 2175(5)

Re(1)-Cl(1) 2271(8)

Re(1)-Cl(1) 2337(4)

Ru(1)-C(82) 1807(6)

Ru(1)-C(30) 2013(5)

Ru(1)-O(1) 2194(3)

Ru(1)-O(3) 2236(4)

Ru(1)-P(63) 23781(16)

Ru(1)-P(44) 23806(17)

Ru(1)-C(2) 2564(5)

C(85)-O(85) 1187(8)

C(85)-O(85) 1178(9)

O(1)-C(2) 1255(7)

C(2)-O(3) 1268(7)

C(2)-C(4) 1480(7)

C(4)-C(9) 1377(8)

C(4)-C(5) 1399(8)

C(5)-C(6) 1360(8)

C(6)-C(7) 1376(8)

C(7)-C(8) 1376(8)

C(7)-S(10) 1761(6)

C(8)-C(9) 1392(8)

P(11)-C(18) 1800(6)

P(11)-C(24) 1811(6)

P(11)-C(12) 1824(6)

C(12)-C(13) 1386(8)

C(12)-C(17) 1388(9)

C(13)-C(14) 1360(10)

C(14)-C(15) 1383(11)

C(15)-C(16) 1395(10)

C(16)-C(17) 1366(9)

C(18)-C(23) 1374(9)

C(18)-C(19) 1405(9)

C(19)-C(20) 1388(9)

C(20)-C(21) 1378(10)

C(21)-C(22) 1346(11)

C(30)-Ru(1)-C(2) 1308(2)

O(1)-Ru(1)-C(2) 2928(16)

O(3)-Ru(1)-C(2) 2965(16)

P(63)-Ru(1)-C(2) 8971(14)

P(44)-Ru(1)-C(2) 8897(14)

O(85)-C(85)-Re(1) 1747(13)

O(85)-C(85)-Re(1) 176(4)

C(2)-O(1)-Ru(1) 919(3)

O(1)-C(2)-O(3) 1194(5)

O(1)-C(2)-C(4) 1223(5)

O(3)-C(2)-C(4) 1183(5)

O(1)-C(2)-Ru(1) 588(3)

O(3)-C(2)-Ru(1) 607(3)

C(4)-C(2)-Ru(1) 1784(4)

C(2)-O(3)-Ru(1) 897(3)

C(9)-C(4)-C(5) 1186(5)

C(9)-C(4)-C(2) 1207(5)

C(5)-C(4)-C(2) 1207(6)

C(6)-C(5)-C(4) 1199(6)

C(5)-C(6)-C(7) 1226(6)

C(8)-C(7)-C(6) 1176(5)

C(8)-C(7)-S(10) 1237(5)

C(6)-C(7)-S(10) 1187(5)

C(7)-C(8)-C(9) 1212(6)

C(4)-C(9)-C(8) 1202(6)

C(7)-S(10)-Au(1) 1059(2)

C(18)-P(11)-C(24) 1048(3)

C(18)-P(11)-C(12) 1061(3)

C(24)-P(11)-C(12) 1055(3)

C(18)-P(11)-Au(1) 1112(2)

C(24)-P(11)-Au(1) 1164(2)

C(12)-P(11)-Au(1) 1120(2)

C(13)-C(12)-C(17) 1192(6)

C(13)-C(12)-P(11) 1191(5)

C(17)-C(12)-P(11) 1217(5)

C(14)-C(13)-C(12) 1206(7)

C(13)-C(14)-C(15) 1207(7)

C(14)-C(15)-C(16) 1188(6)

C(17)-C(16)-C(15) 1204(7)

C(16)-C(17)-C(12) 1203(7)

C(23)-C(18)-C(19) 1183(6)

C(23)-C(18)-P(11) 1231(5)

C(19)-C(18)-P(11) 1186(5)

210

C(22)-C(23) 1422(10)

C(24)-C(25) 1378(9)

C(24)-C(29) 1384(8)

C(25)-C(26) 1368(9)

C(26)-C(27) 1380(10)

C(27)-C(28) 1370(10)

C(28)-C(29) 1387(9)

C(30)-C(31) 1331(7)

C(31)-C(34) 1456(8)

N(32)-C(33) 1326(7)

N(32)-C(37) 1356(7)

C(33)-C(34) 1390(8)

C(34)-C(35) 1399(8)

C(35)-C(36) 1363(8)

C(36)-C(37) 1384(8)

C(37)-C(38) 1482(8)

C(38)-N(43) 1341(7)

C(38)-C(39) 1372(8)

C(39)-C(40) 1386(9)

C(40)-C(41) 1364(9)

C(41)-C(42) 1371(9)

C(42)-N(43) 1347(8)

P(44)-C(45) 1819(7)

P(44)-C(57) 1820(7)

P(44)-C(51) 1830(4)

P(44)-C(51) 1861(15)

C(45)-C(46) 1379(10)

C(45)-C(50) 1385(10)

C(46)-C(47) 1356(10)

C(47)-C(48) 1331(14)

C(48)-C(49) 1359(13)

C(49)-C(50) 1397(11)

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(57)-C(58) 1390(9)

C(57)-C(62) 1396(9)

C(58)-C(59) 1396(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1366(10)

C(61)-C(62) 1401(9)

P(63)-C(70) 1812(7)

P(63)-C(76) 1817(9)

P(63)-C(76) 1831(5)

P(63)-C(64) 1831(6)

C(64)-C(65) 1367(9)

C(64)-C(69) 1379(8)

C(65)-C(66) 1381(9)

C(66)-C(67) 1352(9)

C(67)-C(68) 1382(10)

C(68)-C(69) 1394(8)

C(70)-C(75) 1371(10)

C(20)-C(19)-C(18) 1209(6)

C(21)-C(20)-C(19) 1208(7)

C(22)-C(21)-C(20) 1184(7)

C(21)-C(22)-C(23) 1227(7)

C(18)-C(23)-C(22) 1189(7)

C(25)-C(24)-C(29) 1188(6)

C(25)-C(24)-P(11) 1219(5)

C(29)-C(24)-P(11) 1190(5)

C(26)-C(25)-C(24) 1212(6)

C(25)-C(26)-C(27) 1195(7)

C(28)-C(27)-C(26) 1206(7)

C(27)-C(28)-C(29) 1194(7)

C(24)-C(29)-C(28) 1205(7)

C(31)-C(30)-Ru(1) 1354(5)

C(30)-C(31)-C(34) 1249(6)

C(33)-N(32)-C(37) 1176(5)

C(33)-N(32)-Re(1) 1254(4)

C(37)-N(32)-Re(1) 1168(4)

N(32)-C(33)-C(34) 1257(6)

C(33)-C(34)-C(35) 1148(5)

C(33)-C(34)-C(31) 1212(5)

C(35)-C(34)-C(31) 1239(5)

C(36)-C(35)-C(34) 1211(6)

C(35)-C(36)-C(37) 1194(6)

N(32)-C(37)-C(36) 1213(5)

N(32)-C(37)-C(38) 1151(5)

C(36)-C(37)-C(38) 1235(5)

N(43)-C(38)-C(39) 1214(6)

N(43)-C(38)-C(37) 1151(5)

C(39)-C(38)-C(37) 1234(6)

C(38)-C(39)-C(40) 1208(6)

C(41)-C(40)-C(39) 1172(6)

C(40)-C(41)-C(42) 1201(6)

N(43)-C(42)-C(41) 1226(6)

C(38)-N(43)-C(42) 1179(5)

C(38)-N(43)-Re(1) 1180(4)

C(42)-N(43)-Re(1) 1241(4)

C(45)-P(44)-C(57) 1029(3)

C(45)-P(44)-C(51) 1036(4)

C(57)-P(44)-C(51) 1002(4)

C(45)-P(44)-C(51) 1043(12)

C(57)-P(44)-C(51) 1099(10)

C(45)-P(44)-Ru(1) 1140(2)

C(57)-P(44)-Ru(1) 1181(2)

C(51)-P(44)-Ru(1) 1160(3)

C(51)-P(44)-Ru(1) 1068(12)

C(46)-C(45)-C(50) 1180(7)

C(46)-C(45)-P(44) 1194(6)

C(50)-C(45)-P(44) 1226(6)

C(47)-C(46)-C(45) 1219(8)

C(48)-C(47)-C(46) 1204(9)

C(47)-C(48)-C(49) 1203(8)

C(48)-C(49)-C(50) 1208(9)

C(45)-C(50)-C(49) 1186(8)

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1173(4)

C(56)-C(51)-P(44) 1227(4)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

211

C(70)-C(71) 1386(9)

C(71)-C(72) 1392(12)

C(72)-C(73) 1341(13)

C(73)-C(74) 1368(13)

C(74)-C(75) 1396(11)

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(82)-O(82) 1152(7)

C(83)-O(83) 1152(7)

C(84)-O(84) 1138(8)

P(11)-Au(1)-S(10) 17634(6)

C(83)-Re(1)-C(84) 865(3)

C(83)-Re(1)-C(85) 861(15)

C(84)-Re(1)-C(85) 924(15)

C(83)-Re(1)-C(85) 896(5)

C(84)-Re(1)-C(85) 887(5)

C(83)-Re(1)-N(43) 1003(2)

C(84)-Re(1)-N(43) 1732(2)

C(85)-Re(1)-N(43) 884(14)

C(85)-Re(1)-N(43) 910(5)

C(83)-Re(1)-N(32) 1743(2)

C(84)-Re(1)-N(32) 986(2)

C(85)-Re(1)-N(32) 913(15)

C(85)-Re(1)-N(32) 930(5)

N(43)-Re(1)-N(32) 7463(18)

C(83)-Re(1)-Cl(1) 974(3)

C(84)-Re(1)-Cl(1) 941(3)

C(85)-Re(1)-Cl(1) 1729(14)

N(43)-Re(1)-Cl(1) 848(2)

N(32)-Re(1)-Cl(1) 847(2)

C(83)-Re(1)-Cl(1) 873(3)

C(84)-Re(1)-Cl(1) 926(3)

C(85)-Re(1)-Cl(1) 1766(5)

N(43)-Re(1)-Cl(1) 8805(17)

N(32)-Re(1)-Cl(1) 8998(17)

C(82)-Ru(1)-C(30) 917(3)

C(82)-Ru(1)-O(1) 1667(2)

C(30)-Ru(1)-O(1) 10156(19)

C(82)-Ru(1)-O(3) 1078(2)

C(30)-Ru(1)-O(3) 1604(2)

O(1)-Ru(1)-O(3) 5893(14)

C(82)-Ru(1)-P(63) 8796(19)

C(30)-Ru(1)-P(63) 9106(17)

O(1)-Ru(1)-P(63) 9197(11)

O(3)-Ru(1)-P(63) 8801(11)

C(82)-Ru(1)-P(44) 9536(19)

C(30)-Ru(1)-P(44) 8717(17)

O(1)-Ru(1)-P(44) 8519(11)

O(3)-Ru(1)-P(44) 9255(11)

P(63)-Ru(1)-P(44) 17628(6)

C(55)-C(56)-C(51) 1200

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1203(18)

C(56)-C(51)-P(44) 1196(18)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

C(55)-C(56)-C(51) 1200

C(58)-C(57)-C(62) 1183(6)

C(58)-C(57)-P(44) 1217(6)

C(62)-C(57)-P(44) 1199(5)

C(57)-C(58)-C(59) 1199(8)

C(60)-C(59)-C(58) 1211(8)

C(61)-C(60)-C(59) 1200(7)

C(60)-C(61)-C(62) 1198(7)

C(57)-C(62)-C(61) 1208(7)

C(70)-P(63)-C(76) 1091(6)

C(70)-P(63)-C(76) 1009(4)

C(70)-P(63)-C(64) 1038(3)

C(76)-P(63)-C(64) 1055(7)

C(76)-P(63)-C(64) 1038(5)

C(70)-P(63)-Ru(1) 1150(2)

C(76)-P(63)-Ru(1) 1081(6)

C(76)-P(63)-Ru(1) 1166(4)

C(64)-P(63)-Ru(1) 11489(19)

C(65)-C(64)-C(69) 1180(6)

C(65)-C(64)-P(63) 1231(4)

C(69)-C(64)-P(63) 1189(5)

C(64)-C(65)-C(66) 1216(6)

C(67)-C(66)-C(65) 1204(7)

C(66)-C(67)-C(68) 1196(6)

C(67)-C(68)-C(69) 1195(6)

C(64)-C(69)-C(68) 1208(7)

C(75)-C(70)-C(71) 1178(7)

C(75)-C(70)-P(63) 1200(5)

C(71)-C(70)-P(63) 1221(6)

C(70)-C(71)-C(72) 1205(8)

C(73)-C(72)-C(71) 1195(8)

C(72)-C(73)-C(74) 1225(9)

C(73)-C(74)-C(75) 1173(10)

C(70)-C(75)-C(74) 1223(8)

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1210(6)

C(81)-C(76)-P(63) 1190(6)

C(76)-C(77)-C(78) 1200

C(79)-C(78)-C(77) 1200

C(78)-C(79)-C(80) 1200

C(81)-C(80)-C(79) 1200

C(80)-C(81)-C(76) 1200

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1215(10)

C(81)-C(76)-P(63) 1184(10)

C(78)-C(77)-C(76) 1200

C(77)-C(78)-C(79) 1200

C(80)-C(79)-C(78) 1200

C(79)-C(80)-C(81) 1200

C(80)-C(81)-C(76) 1200

O(82)-C(82)-Ru(1) 1771(5)

O(83)-C(83)-Re(1) 1771(7)

O(84)-C(84)-Re(1) 1793(6)

212

C(82)-Ru(1)-C(2) 1374(2)










b = 155218(4) Aring = 107289(3)deg

c = 268129(9) Aring = 90deg




F(000) 3784






213












Pd(1)-P(2) 22948(10)

Pd(1)-P(1) 23232(10)

Pd(1)-S(3) 23304(10)

Pd(1)-S(1) 23536(10)

Pd(2)-P(4) 22985(10)

Pd(2)-S(12) 23240(10)

Pd(2)-P(3) 23292(10)

Pd(2)-S(10) 23512(10)

P(1)-C(13) 1814(4)

P(1)-C(25) 1815(4)

P(1)-C(19) 1818(4)

P(2)-C(31) 1809(4)

P(2)-C(43) 1810(4)

P(2)-C(37) 1823(4)

P(3)-C(49) 1805(4)

P(3)-C(61) 1822(4)

P(3)-C(55) 1822(4)

P(4)-C(79) 1818(4)

P(4)-C(67) 1821(4)

P(4)-C(73) 1826(4)

S(1)-C(2) 1735(4)

C(2)-N(4) 1302(5)

C(2)-S(3) 1722(4)

N(4)-C(5) 1458(5)

N(4)-C(9) 1478(5)

C(5)-C(6) 1524(6)

C(6)-N(7) 1473(5)

N(7)-C(11) 1308(5)

N(7)-C(8) 1464(5)

C(8)-C(9) 1511(6)

S(10)-C(11) 1728(4)

C(11)-S(12) 1717(4)

C(13)-C(18) 1380(6)

C(13)-C(14) 1383(6)

C(14)-C(15) 1384(7)

C(15)-C(16) 1371(8)

C(16)-C(17) 1341(8)

C(17)-C(18) 1383(7)

C(19)-C(24) 1371(6)

C(19)-C(20) 1392(6)

C(20)-C(21) 1372(7)

C(79)-P(4)-C(73) 9763(18)

C(67)-P(4)-C(73) 1063(2)

C(79)-P(4)-Pd(2) 11555(13)

C(67)-P(4)-Pd(2) 10862(13)

C(73)-P(4)-Pd(2) 11746(14)

C(2)-S(1)-Pd(1) 8607(13)

N(4)-C(2)-S(3) 1232(3)

N(4)-C(2)-S(1) 1256(3)

S(3)-C(2)-S(1) 1112(2)

C(2)-S(3)-Pd(1) 8709(14)

C(2)-N(4)-C(5) 1228(3)

C(2)-N(4)-C(9) 1227(3)

C(5)-N(4)-C(9) 1145(3)

N(4)-C(5)-C(6) 1090(3)

N(7)-C(6)-C(5) 1095(3)

C(11)-N(7)-C(8) 1244(3)

C(11)-N(7)-C(6) 1220(3)

C(8)-N(7)-C(6) 1133(3)

N(7)-C(8)-C(9) 1103(3)

N(4)-C(9)-C(8) 1100(3)

C(11)-S(10)-Pd(2) 8619(13)

N(7)-C(11)-S(12) 1234(3)

N(7)-C(11)-S(10) 1253(3)

S(12)-C(11)-S(10) 1112(2)

C(11)-S(12)-Pd(2) 8729(13)

C(18)-C(13)-C(14) 1183(4)

C(18)-C(13)-P(1) 1234(3)

C(14)-C(13)-P(1) 1183(3)

C(13)-C(14)-C(15) 1211(5)

C(16)-C(15)-C(14) 1195(5)

C(17)-C(16)-C(15) 1194(5)

C(16)-C(17)-C(18) 1223(5)

C(13)-C(18)-C(17) 1192(5)

C(24)-C(19)-C(20) 1199(4)

C(24)-C(19)-P(1) 1194(3)

C(20)-C(19)-P(1) 1207(4)

C(21)-C(20)-C(19) 1199(5)

C(22)-C(21)-C(20) 1206(6)

C(21)-C(22)-C(23) 1211(5)

C(22)-C(23)-C(24) 1187(6)

214

C(21)-C(22) 1342(9)

C(22)-C(23) 1390(9)

C(23)-C(24) 1402(7)

C(25)-C(30) 1390(5)

C(25)-C(26) 1405(5)

C(26)-C(27) 1377(6)

C(27)-C(28) 1380(6)

C(28)-C(29) 1375(6)

C(29)-C(30) 1380(6)

C(31)-C(32) 1390(6)

C(31)-C(36) 1392(6)

C(32)-C(33) 1387(6)

C(33)-C(34) 1380(8)

C(34)-C(35) 1365(8)

C(35)-C(36) 1384(7)

C(37)-C(42) 1379(6)

C(37)-C(38) 1388(6)

C(38)-C(39) 1382(6)

C(39)-C(40) 1367(7)

C(40)-C(41) 1356(7)

C(41)-C(42) 1386(6)

C(43)-C(44) 1381(6)

C(43)-C(48) 1393(6)

C(44)-C(45) 1394(7)

C(45)-C(46) 1373(8)

C(46)-C(47) 1365(8)

C(47)-C(48) 1390(6)

C(49)-C(50) 1388(5)

C(49)-C(54) 1402(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1360(6)

C(52)-C(53) 1384(6)

C(53)-C(54) 1372(6)

C(55)-C(56) 1390(5)

C(55)-C(60) 1393(5)

C(56)-C(57) 1385(6)

C(57)-C(58) 1374(6)

C(58)-C(59) 1375(6)

C(59)-C(60) 1377(6)

C(61)-C(66) 1393(6)

C(61)-C(62) 1394(6)

C(62)-C(63) 1388(6)

C(63)-C(64) 1379(7)

C(64)-C(65) 1373(7)

C(65)-C(66) 1384(6)

C(67)-C(72) 1387(6)

C(67)-C(68) 1387(6)

C(68)-C(69) 1378(6)

C(69)-C(70) 1362(7)

C(70)-C(71) 1375(8)

C(71)-C(72) 1376(7)

C(73)-C(78) 1371(6)

C(73)-C(74) 1392(6)

C(74)-C(75) 1371(7)

C(75)-C(76) 1369(8)

C(76)-C(77) 1376(8)

C(77)-C(78) 1410(6)

C(79)-C(84) 1384(5)

C(79)-C(80) 1394(5)

C(80)-C(81) 1374(6)

C(81)-C(82) 1387(6)

C(19)-C(24)-C(23) 1198(5)

C(30)-C(25)-C(26) 1184(4)

C(30)-C(25)-P(1) 1208(3)

C(26)-C(25)-P(1) 1207(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1200(4)

C(29)-C(28)-C(27) 1201(4)

C(28)-C(29)-C(30) 1205(4)

C(29)-C(30)-C(25) 1204(4)

C(32)-C(31)-C(36) 1193(4)

C(32)-C(31)-P(2) 1192(3)

C(36)-C(31)-P(2) 1214(4)

C(33)-C(32)-C(31) 1204(5)

C(34)-C(33)-C(32) 1195(5)

C(35)-C(34)-C(33) 1205(5)

C(34)-C(35)-C(36) 1207(5)

C(35)-C(36)-C(31) 1196(5)

C(42)-C(37)-C(38) 1188(4)

C(42)-C(37)-P(2) 1230(3)

C(38)-C(37)-P(2) 1180(3)

C(39)-C(38)-C(37) 1200(4)

C(40)-C(39)-C(38) 1204(5)

C(41)-C(40)-C(39) 1201(4)

C(40)-C(41)-C(42) 1204(5)

C(37)-C(42)-C(41) 1203(4)

C(44)-C(43)-C(48) 1202(4)

C(44)-C(43)-P(2) 1243(4)

C(48)-C(43)-P(2) 1154(3)

C(43)-C(44)-C(45) 1192(5)

C(46)-C(45)-C(44) 1201(5)

C(47)-C(46)-C(45) 1211(5)

C(46)-C(47)-C(48) 1196(5)

C(47)-C(48)-C(43) 1198(5)

C(50)-C(49)-C(54) 1191(4)

C(50)-C(49)-P(3) 1196(3)

C(54)-C(49)-P(3) 1212(3)

C(49)-C(50)-C(51) 1197(4)

C(52)-C(51)-C(50) 1202(4)

C(51)-C(52)-C(53) 1209(4)

C(54)-C(53)-C(52) 1197(4)

C(53)-C(54)-C(49) 1204(4)

C(56)-C(55)-C(60) 1185(4)

C(56)-C(55)-P(3) 1219(3)

C(60)-C(55)-P(3) 1193(3)

C(57)-C(56)-C(55) 1200(4)

C(58)-C(57)-C(56) 1208(4)

C(57)-C(58)-C(59) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(59)-C(60)-C(55) 1209(4)

C(66)-C(61)-C(62) 1187(4)

C(66)-C(61)-P(3) 1201(3)

C(62)-C(61)-P(3) 1211(3)

C(63)-C(62)-C(61) 1199(4)

C(64)-C(63)-C(62) 1208(5)

C(65)-C(64)-C(63) 1194(4)

C(64)-C(65)-C(66) 1207(5)

C(65)-C(66)-C(61) 1204(4)

C(72)-C(67)-C(68) 1191(4)

C(72)-C(67)-P(4) 1188(3)

C(68)-C(67)-P(4) 1215(3)

C(69)-C(68)-C(67) 1199(5)

215

C(82)-C(83) 1375(6)

C(83)-C(84) 1368(5)

P(10)-F(13) 1549(4)

P(10)-F(15) 1560(4)

P(10)-F(14) 1560(3)

P(10)-F(12) 1564(4)

P(10)-F(11) 1582(3)

P(10)-F(16) 1592(3)

P(20)-F(23) 1557(3)

P(20)-F(21) 1565(3)

P(20)-F(26) 1573(3)

P(20)-F(24) 1582(3)

P(20)-F(22) 1584(3)

P(20)-F(25) 1589(3)

O(90)-C(91) 1361(6)

O(90)-C(93) 1397(7)

C(91)-C(92) 1483(8)

C(93)-C(94) 1393(8)

O(90)-C(91) 1341(10)

O(90)-C(93) 1345(10)

C(91)-C(92) 1452(10)

C(93)-C(94) 1451(10)

P(2)-Pd(1)-P(1) 10098(4)

P(2)-Pd(1)-S(3) 16943(4)

P(1)-Pd(1)-S(3) 8822(4)

P(2)-Pd(1)-S(1) 9507(4)

P(1)-Pd(1)-S(1) 16140(4)

S(3)-Pd(1)-S(1) 7504(4)

P(4)-Pd(2)-S(12) 17025(4)

P(4)-Pd(2)-P(3) 10004(4)

S(12)-Pd(2)-P(3) 8970(3)

P(4)-Pd(2)-S(10) 9535(3)

S(12)-Pd(2)-S(10) 7490(3)

P(3)-Pd(2)-S(10) 16452(4)

C(13)-P(1)-C(25) 10983(18)

C(13)-P(1)-C(19) 1033(2)

C(25)-P(1)-C(19) 10175(19)

C(13)-P(1)-Pd(1) 10736(14)

C(25)-P(1)-Pd(1) 10878(12)

C(19)-P(1)-Pd(1) 12519(13)

C(31)-P(2)-C(43) 10980(19)

C(31)-P(2)-C(37) 10173(17)

C(43)-P(2)-C(37) 10461(19)

C(31)-P(2)-Pd(1) 11826(15)

C(43)-P(2)-Pd(1) 10682(14)

C(37)-P(2)-Pd(1) 11481(13)

C(49)-P(3)-C(61) 10500(18)

C(49)-P(3)-C(55) 10370(18)

C(61)-P(3)-C(55) 10515(18)

C(49)-P(3)-Pd(2) 11419(12)

C(61)-P(3)-Pd(2) 11999(13)

C(55)-P(3)-Pd(2) 10732(12)

C(79)-P(4)-C(67) 11063(18)

C(70)-C(69)-C(68) 1209(5)

C(69)-C(70)-C(71) 1194(5)

C(70)-C(71)-C(72) 1209(5)

C(71)-C(72)-C(67) 1197(5)

C(78)-C(73)-C(74) 1201(4)

C(78)-C(73)-P(4) 1194(3)

C(74)-C(73)-P(4) 1189(3)

C(75)-C(74)-C(73) 1205(5)

C(76)-C(75)-C(74) 1197(5)

C(75)-C(76)-C(77) 1209(5)

C(76)-C(77)-C(78) 1196(5)

C(73)-C(78)-C(77) 1191(5)

C(84)-C(79)-C(80) 1198(4)

C(84)-C(79)-P(4) 1151(3)

C(80)-C(79)-P(4) 1246(3)

C(81)-C(80)-C(79) 1192(4)

C(80)-C(81)-C(82) 1206(4)

C(83)-C(82)-C(81) 1199(4)

C(84)-C(83)-C(82) 1201(4)

C(83)-C(84)-C(79) 1205(4)

F(13)-P(10)-F(15) 1779(3)

F(13)-P(10)-F(14) 913(3)

F(15)-P(10)-F(14) 902(3)

F(13)-P(10)-F(12) 903(3)

F(15)-P(10)-F(12) 882(3)

F(14)-P(10)-F(12) 1775(3)

F(13)-P(10)-F(11) 914(2)

F(15)-P(10)-F(11) 901(2)

F(14)-P(10)-F(11) 915(2)

F(12)-P(10)-F(11) 903(2)

F(13)-P(10)-F(16) 891(2)

F(15)-P(10)-F(16) 8948(19)

F(14)-P(10)-F(16) 8896(18)

F(12)-P(10)-F(16) 892(2)

F(11)-P(10)-F(16) 1793(2)

F(23)-P(20)-F(21) 896(2)

F(23)-P(20)-F(26) 923(2)

F(21)-P(20)-F(26) 1778(2)

F(23)-P(20)-F(24) 9177(19)

F(21)-P(20)-F(24) 8826(17)

F(26)-P(20)-F(24) 9056(16)

F(23)-P(20)-F(22) 893(2)

F(21)-P(20)-F(22) 9091(19)

F(26)-P(20)-F(22) 9024(18)

F(24)-P(20)-F(22) 1787(2)

F(23)-P(20)-F(25) 1794(2)

F(21)-P(20)-F(25) 908(2)

F(26)-P(20)-F(25) 873(2)

F(24)-P(20)-F(25) 8868(19)

F(22)-P(20)-F(25) 903(2)

C(91)-O(90)-C(93) 1125(6)

O(90)-C(91)-C(92) 1100(6)

C(94)-C(93)-O(90) 1137(7)

C(91)-O(90)-C(93) 119(2)

O(90)-C(91)-C(92) 1157(17)

O(90)-C(93)-C(94) 1167(17)

216










b = 107032(4) Aring = 78500(4)deg

c = 212565(12) Aring = 88333(3)deg




F(000) 946









217









Pd(1)-P(2) 22888(9)

Pd(1)-P(1) 23146(9)

Pd(1)-S(1) 23388(8)

Pd(1)-S(3) 23479(9)

P(1)-C(7) 1816(4)

P(1)-C(13) 1817(3)

P(1)-C(19) 1825(4)

P(2)-C(25) 1809(4)

P(2)-C(37) 1821(4)

P(2)-C(31) 1822(4)

S(1)-C(2) 1727(4)

C(2)-N(4) 1326(4)

C(2)-S(3) 1714(4)

N(4)-C(5) 1463(5)

N(4)-C(6) 1480(5)

C(5)-C(6)1 1519(6)

C(6)-C(5)1 1519(6)

C(7)-C(8) 1398(6)

C(7)-C(12) 1399(5)

C(8)-C(9) 1378(6)

C(9)-C(10) 1379(7)

C(10)-C(11) 1390(8)

C(11)-C(12) 1369(7)

C(13)-C(14) 1386(6)

C(13)-C(18) 1392(5)

C(14)-C(15) 1389(5)

C(15)-C(16) 1380(6)

C(16)-C(17) 1381(7)

C(17)-C(18) 1397(5)

C(19)-C(24) 1383(6)

C(19)-C(20) 1386(6)

C(20)-C(21) 1388(6)

C(21)-C(22) 1375(8)

C(22)-C(23) 1370(9)

C(23)-C(24) 1407(7)

C(25)-C(30) 1394(6)

C(25)-C(26) 1396(6)

C(26)-C(27) 1379(6)

C(27)-C(28) 1384(8)

C(28)-C(29) 1365(8)

C(29)-C(30) 1395(6)

C(31)-C(32) 1389(5)

C(31)-C(36) 1391(5)

C(32)-C(33) 1392(6)

C(33)-C(34) 1377(7)

C(34)-C(35) 1377(6)

C(8)-C(7)-P(1) 1204(3)

C(12)-C(7)-P(1) 1209(3)

C(9)-C(8)-C(7) 1203(4)

C(8)-C(9)-C(10) 1202(5)

C(9)-C(10)-C(11) 1199(5)

C(12)-C(11)-C(10) 1202(4)

C(11)-C(12)-C(7) 1205(4)

C(14)-C(13)-C(18) 1191(3)

C(14)-C(13)-P(1) 1215(3)

C(18)-C(13)-P(1) 1194(3)

C(13)-C(14)-C(15) 1204(4)

C(16)-C(15)-C(14) 1202(4)

C(15)-C(16)-C(17) 1202(4)

C(16)-C(17)-C(18) 1196(4)

C(13)-C(18)-C(17) 1204(4)

C(24)-C(19)-C(20) 1194(4)

C(24)-C(19)-P(1) 1224(3)

C(20)-C(19)-P(1) 1182(3)

C(19)-C(20)-C(21) 1209(5)

C(22)-C(21)-C(20) 1197(5)

C(23)-C(22)-C(21) 1201(5)

C(22)-C(23)-C(24) 1207(5)

C(19)-C(24)-C(23) 1192(5)

C(30)-C(25)-C(26) 1191(4)

C(30)-C(25)-P(2) 1230(3)

C(26)-C(25)-P(2) 1176(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1197(5)

C(29)-C(28)-C(27) 1206(4)

C(28)-C(29)-C(30) 1204(5)

C(25)-C(30)-C(29) 1196(4)

C(32)-C(31)-C(36) 1189(4)

C(32)-C(31)-P(2) 1257(3)

C(36)-C(31)-P(2) 1153(3)

C(31)-C(32)-C(33) 1198(4)

C(34)-C(33)-C(32) 1207(4)

C(35)-C(34)-C(33) 1198(4)

C(34)-C(35)-C(36) 1200(4)

C(35)-C(36)-C(31) 1207(4)

C(42)-C(37)-C(38) 1184(4)

C(42)-C(37)-P(2) 1189(3)

C(38)-C(37)-P(2) 1227(3)

C(39)-C(38)-C(37) 1197(5)

C(40)-C(39)-C(38) 1206(5)

C(39)-C(40)-C(41) 1208(5)

C(40)-C(41)-C(42) 1197(5)

218

C(35)-C(36) 1387(6)

C(37)-C(42) 1385(6)

C(37)-C(38) 1399(6)

C(38)-C(39) 1392(6)

C(39)-C(40) 1360(8)

C(40)-C(41) 1361(8)

C(41)-C(42) 1394(7)

P(10)-F(14) 1578(10)

P(10)-F(13) 1579(10)

P(10)-F(16) 1597(10)

P(10)-F(12) 1598(10)

P(10)-F(15) 1599(10)

P(10)-F(11) 1614(10)

P(10)-F(11) 1588(13)

P(10)-F(13) 1591(13)

P(10)-F(14) 1592(13)

P(10)-F(12) 1593(13)

P(10)-F(16) 1595(13)

P(10)-F(15) 1598(13)

P(20)-F(25) 1551(11)

P(20)-F(24) 1557(12)

P(20)-F(26) 1563(11)

P(20)-F(22) 1566(11)

P(20)-F(21) 1575(11)

P(20)-F(23) 1585(11)

P(20)-F(23) 1521(11)

P(20)-F(21) 1545(11)

P(20)-F(26) 1559(11)

P(20)-F(24) 1560(11)

P(20)-F(22) 1585(11)

P(20)-F(25) 1628(11)

P(2)-Pd(1)-P(1) 9715(3)

P(2)-Pd(1)-S(1) 9505(3)

P(1)-Pd(1)-S(1) 16705(3)

P(2)-Pd(1)-S(3) 16837(3)

P(1)-Pd(1)-S(3) 9298(3)

S(1)-Pd(1)-S(3) 7536(3)

C(7)-P(1)-C(13) 10326(17)

C(7)-P(1)-C(19) 10743(19)

C(13)-P(1)-C(19) 10434(17)

C(7)-P(1)-Pd(1) 11069(13)

C(13)-P(1)-Pd(1) 12157(12)

C(19)-P(1)-Pd(1) 10864(13)

C(25)-P(2)-C(37) 10169(18)

C(25)-P(2)-C(31) 11326(17)

C(37)-P(2)-C(31) 10528(17)

C(25)-P(2)-Pd(1) 11377(13)

C(37)-P(2)-Pd(1) 11311(12)

C(31)-P(2)-Pd(1) 10929(13)

C(2)-S(1)-Pd(1) 8589(12)

N(4)-C(2)-S(3) 1233(3)

N(4)-C(2)-S(1) 1239(3)

S(3)-C(2)-S(1) 11276(19)

C(2)-S(3)-Pd(1) 8590(13)

C(2)-N(4)-C(5) 1234(3)

C(2)-N(4)-C(6) 1228(3)

C(5)-N(4)-C(6) 1133(3)

N(4)-C(5)-C(6)1 1090(3)

N(4)-C(6)-C(5)1 1087(3)

C(8)-C(7)-C(12) 1188(4)

C(37)-C(42)-C(41) 1208(4)

F(14)-P(10)-F(13) 910(7)

F(14)-P(10)-F(16) 912(6)

F(13)-P(10)-F(16) 912(6)

F(14)-P(10)-F(12) 1781(8)

F(13)-P(10)-F(12) 901(7)

F(16)-P(10)-F(12) 904(7)

F(14)-P(10)-F(15) 902(7)

F(13)-P(10)-F(15) 1783(8)

F(16)-P(10)-F(15) 901(7)

F(12)-P(10)-F(15) 886(7)

F(14)-P(10)-F(11) 901(7)

F(13)-P(10)-F(11) 894(7)

F(16)-P(10)-F(11) 1785(9)

F(12)-P(10)-F(11) 883(6)

F(15)-P(10)-F(11) 893(6)

F(11)-P(10)-F(13) 904(8)

F(11)-P(10)-F(14) 902(8)

F(13)-P(10)-F(14) 903(8)

F(11)-P(10)-F(12) 902(8)

F(13)-P(10)-F(12) 901(8)

F(14)-P(10)-F(12) 1795(11)

F(11)-P(10)-F(16) 1794(11)

F(13)-P(10)-F(16) 902(8)

F(14)-P(10)-F(16) 899(8)

F(12)-P(10)-F(16) 897(8)

F(11)-P(10)-F(15) 898(8)

F(13)-P(10)-F(15) 1798(12)

F(14)-P(10)-F(15) 899(8)

F(12)-P(10)-F(15) 897(8)

F(16)-P(10)-F(15) 896(8)

F(25)-P(20)-F(24) 911(7)

F(25)-P(20)-F(26) 923(7)

F(24)-P(20)-F(26) 911(7)

F(25)-P(20)-F(22) 916(7)

F(24)-P(20)-F(22) 1766(10)

F(26)-P(20)-F(22) 908(7)

F(25)-P(20)-F(21) 899(7)

F(24)-P(20)-F(21) 902(8)

F(26)-P(20)-F(21) 1774(9)

F(22)-P(20)-F(21) 878(7)

F(25)-P(20)-F(23) 1786(10)

F(24)-P(20)-F(23) 894(7)

F(26)-P(20)-F(23) 890(7)

F(22)-P(20)-F(23) 879(7)

F(21)-P(20)-F(23) 888(7)

F(23)-P(20)-F(21) 941(7)

F(23)-P(20)-F(26) 932(7)

F(21)-P(20)-F(26) 1724(8)

F(23)-P(20)-F(24) 939(7)

F(21)-P(20)-F(24) 907(7)

F(26)-P(20)-F(24) 910(7)

F(23)-P(20)-F(22) 931(7)

F(21)-P(20)-F(22) 887(7)

F(26)-P(20)-F(22) 886(7)

F(24)-P(20)-F(22) 1730(8)

F(23)-P(20)-F(25) 1771(9)

F(21)-P(20)-F(25) 878(7)

F(26)-P(20)-F(25) 849(7)

F(24)-P(20)-F(25) 883(7)

F(22)-P(20)-F(25) 847(6)

219










b = 1085381(18) Aring = 1065109(16)deg

c = 267343(4) Aring = 90deg




F(000) 4112








220











Pd(1)-P(2) 22811(15)

Pd(1)-S(1) 23190(15)

Pd(1)-P(1) 23297(15)

Pd(1)-S(3) 23720(16)

Pd(2)-P(4) 22915(17)

Pd(2)-S(9) 23180(15)

Pd(2)-P(3) 23298(16)

Pd(2)-S(10) 23735(17)

P(1)-C(37) 1820(7)

P(1)-C(25) 1826(7)

P(1)-C(31) 1832(7)

P(2)-C(43) 1814(6)

P(2)-C(49) 1820(6)

P(2)-C(55) 1826(7)

P(3)-C(61) 1832(9)

P(3)-C(67) 1832(7)

P(3)-C(73) 1837(7)

P(4)-C(85) 1815(7)

P(4)-C(79) 1829(7)

P(4)-C(91) 1833(6)

S(1)-C(2) 1715(7)

C(2)-N(4) 1323(8)

C(2)-S(3) 1718(6)

N(4)-C(5) 1470(8)

N(4)-C(11) 1475(8)

C(5)-C(6) 1518(8)

C(6)-N(7) 1487(8)

N(7)-C(8) 1316(9)

N(7)-C(18) 1463(9)

C(8)-S(9) 1722(7)

C(8)-S(10) 1727(7)

C(11)-C(12) 1500(9)

C(12)-C(13) 1376(11)

C(12)-C(17) 1378(10)

C(13)-C(14) 1385(12)

C(14)-C(15) 1393(14)

C(15)-C(16) 1363(14)

C(16)-C(17) 1377(13)

C(18)-C(19) 1510(11)

C(19)-C(24) 1374(12)

C(19)-C(20) 1406(11)

C(20)-C(21) 1390(15)

C(21)-C(22) 1352(18)

C(22)-C(23) 1395(16)

C(79)-P(4)-Pd(2) 1116(2)

C(91)-P(4)-Pd(2) 1124(20

C(2)-S(1)-Pd(1) 859(2)

N(4)-C(2)-S(1) 1227(5)

N(4)-C(2)-S(3) 1240(5)

S(1)-C(2)-S(3) 1132(4)

C(2)-S(3)-Pd(1) 842(2)

C(2)-N(4)-C(5) 1214(5)

C(2)-N(4)-C(11) 1207(5)

C(5)-N(4)-C(11) 1176(5)

N(4)-C(5)-C(6) 1104(5)

N(7)-C(6)-C(5) 1085(5)

C(8)-N(7)-C(18) 1229(6)

C(8)-N(7)-C(6) 1194(6)

C(18)-N(7)-C(6) 1177(5)

N(7)-C(8)-S(9) 1234(5)

N(7)-C(8)-S(10) 1247(5)

S(9)-C(8)-S(10) 1119(4)

C(8)-S(9)-Pd(2) 873(2)

C(8)-S(10)-Pd(2) 854(2)

N(4)-C(11)-C(12) 1154(5)

C(13)-C(12)-C(17) 1187(7)

C(13)-C(12)-C(11) 1218(6)

C(17)-C(12)-C(11) 1193(6)

C(12)-C(13)-C(14) 1206(8)

C(13)-C(14)-C(15) 1203(9)

C(16)-C(15)-C(14) 1185(8)

C(15)-C(16)-C(17) 1214(8)

C(16)-C(17)-C(12) 1206(8)

N(7)-C(18)-C(19) 1127(6)

C(24)-C(19)-C(20) 1180(8)

C(24)-C(19)-C(18) 1234(7)

C(20)-C(19)-C(18) 1185(8)

C(21)-C(20)-C(19) 1189(10)

C(22)-C(21)-C(20) 1229(9)

C(21)-C(22)-C(23) 1187(10)

C(24)-C(23)-C(22) 1193(10)

C(19)-C(24)-C(23) 1222(8)

C(30)-C(25)-C(26) 1194(6)

C(30)-C(25)-P(1) 1211(5)

C(26)-C(25)-P(1) 1194(5)

C(27)-C(26)-C(25) 1195(7)

C(28)-C(27)-C(26) 1206(7)

221

C(23)-C(24) 1389(12)

C(25)-C(30) 1387(10)

C(25)-C(26) 1396(9)

C(26)-C(27) 1392(10)

C(27)-C(28) 1372(12)

C(28)-C(29) 1373(12)

C(29)-C(30) 1391(10)

C(31)-C(32) 1392(9)

C(31)-C(36) 1404(9)

C(32)-C(33) 1390(10)

C(33)-C(34) 1390(13)

C(34)-C(35) 1368(13)

C(35)-C(36) 1396(11)

C(37)-C(42) 1387(10)

C(37)-C(38) 1393(10)

C(38)-C(39) 1387(10)

C(39)-C(40) 1361(12)

C(40)-C(41) 1385(12)

C(41)-C(42) 1390(10)

C(43)-C(48) 1396(10)

C(43)-C(44) 1400(10)

C(44)-C(45) 1370(10)

C(45)-C(46) 1379(12)

C(46)-C(47) 1382(13)

C(47)-C(48) 1400(11)

C(49)-C(54) 1384(11)

C(49)-C(50) 1400(10)

C(50)-C(51) 1380(9)

C(51)-C(52) 1377(14)

C(52)-C(53) 1362(15)

C(53)-C(54) 1399(11)

C(55)-C(60) 1380(9)

C(55)-C(56) 1407(9)

C(56)-C(57) 1370(10)

C(57)-C(58) 1381(11)

C(58)-C(59) 1402(12)

C(59)-C(60) 1373(11)

C(61)-C(62) 1375(11)

C(61)-C(66) 1404(11)

C(62)-C(63) 1395(11)

C(63)-C(64) 1402(14)

C(64)-C(65) 1358(16)

C(65)-C(66) 1377(14)

C(67)-C(68) 1379(11)

C(67)-C(72) 1401(11)

C(68)-C(69) 1386(11)

C(69)-C(70) 1394(14)

C(70)-C(71) 1376(15)

C(71)-C(72) 1391(12)

C(73)-C(78) 1391(11)

C(73)-C(74) 1400(9)

C(74)-C(75) 1393(13)

C(75)-C(76) 1391(14)

C(76)-C(77) 1394(12)

C(77)-C(78) 1384(13)

C(79)-C(84) 1376(11)

C(79)-C(80) 1402(10)

C(80)-C(81) 1399(10)

C(81)-C(82) 1371(13)

C(82)-C(83) 1384(12)

C(83)-C(84) 1379(10)

C(27)-C(28)-C(29) 1202(7)

C(28)-C(29)-C(30) 1202(7)

C(25)-C(30)-C(29) 1201(7)

C(32)-C(31)-C(36) 1189(6)

C(32)-C(31)-P(1) 1203(5)

C(36)-C(31)-P(1) 1208(5)

C(33)-C(32)-C(31) 1208(7)

C(32)-C(33)-C(34) 1204(7)

C(35)-C(34)-C(33) 1187(7)

C(34)-C(35)-C(36) 1224(7)

C(35)-C(36)-C(31) 1188(7)

C(42)-C(37)-C(38) 1181(6)

C(42)-C(37)-P(1) 1194(5)

C(38)-C(37)-P(1) 1224(5)

C(39)-C(38)-C(37) 1210(7)

C(40)-C(39)-C(38) 1202(7)

C(39)-C(40)-C(41) 1200(7)

C(40)-C(41)-C(42) 1200(7)

C(37)-C(42)-C(41) 1206(7)

C(48)-C(43)-C(44) 1199(6)

C(48)-C(43)-P(2) 1250(6)

C(44)-C(43)-P(2) 1151(5)

C(45)-C(44)-C(43) 1201(7)

C(44)-C(45)-C(46) 1205(7)

C(45)-C(46)-C(47) 1202(7)

C(46)-C(47)-C(48) 1204(7)

C(43)-C(48)-C(47) 1189(8)

C(54)-C(49)-C(50) 1205(6)

C(54)-C(49)-P(2) 1209(6)

C(50)-C(49)-P(2) 1185(5)

C(51)-C(50)-C(49) 1197(7)

C(52)-C(51)-C(50) 1198(8)

C(53)-C(52)-C(51) 1205(7)

C(52)-C(53)-C(54) 1213(8)

C(49)-C(54)-C(53) 1181(8)

C(60)-C(55)-C(56) 1188(6)

C(60)-C(55)-P(2) 1235(5)

C(56)-C(55)-P(2) 1177(5)

C(57)-C(56)-C(55) 1198(6)

C(56)-C(57)-C(58) 1213(7)

C(57)-C(58)-C(59) 1190(7)

C(60)-C(59)-C(58) 1197(7)

C(59)-C(60)-C(55) 1213(7)

C(62)-C(61)-C(66) 1196(8)

C(62)-C(61)-P(3) 1193(6)

C(66)-C(61)-P(3) 1208(7)

C(61)-C(62)-C(63) 1218(8)

C(62)-C(63)-C(64) 1176(9)

C(65)-C(64)-C(63) 1203(8)

C(64)-C(65)-C(66) 1224(9)

C(65)-C(66)-C(61) 1183(9)

C(68)-C(67)-C(72) 1195(7)

C(68)-C(67)-P(3) 1198(6)

C(72)-C(67)-P(3) 1204(6)

C(67)-C(68)-C(69) 1210(8)

C(68)-C(69)-C(70) 1192(8)

C(71)-C(70)-C(69) 1205(8)

C(70)-C(71)-C(72) 1202(9)

C(71)-C(72)-C(67) 1196(9)

C(78)-C(73)-C(74) 1186(7)

C(78)-C(73)-P(3) 1212(5)

222

C(85)-C(90) 1379(11)

C(85)-C(86) 1391(10)

C(86)-C(87) 1391(10)

C(87)-C(88) 1387(15)

C(88)-C(89) 1371(14)

C(89)-C(90) 1390(11)

C(91)-C(92) 1379(9)

C(91)-C(96) 1387(9)

C(92)-C(93) 1393(11)

C(93)-C(94) 1368(12)

C(94)-C(95) 1397(11)

C(95)-C(96) 1375(10)

P(10)-F(11) 1550(6)

P(10)-F(15) 1576(5)

P(10)-F(13) 1584(6)

P(10)-F(14) 1590(6)

P(10)-F(12) 1600(5)

P(10)-F(16) 1600(7)

P(20)-F(26) 1543(8)

P(20)-F(21) 1565(8)

P(20)-F(25) 1565(5)

P(20)-F(22) 1568(6)

P(20)-F(24) 1571(6)

P(20)-F(23) 1581(5)

P(2)-Pd(1)-S(1) 9072(5)

P(2)-Pd(1)-P(1) 9793(6)

S(1)-Pd(1)-P(1) 16824(5)

P(2)-Pd(1)-S(3) 16550(6)

S(1)-Pd(1)-S(3) 7528(5)

P(1)-Pd(1)-S(3) 9647(5)

P(4)-Pd(2)-S(9) 9136(5)

P(4)-Pd(2)-P(3) 9795(6)

S(9)-Pd(2)-P(3) 17015(6)

P(4)-Pd(2)-S(10) 16641(6)

S(9)-Pd(2)-S(10) 7505(5)

P(3)-Pd(2)-S(10) 9564(6)

C(37)-P(1)-C(25) 1061(3)

C(37)-P(1)-C(31) 1040(3)

C(25)-P(1)-C(31) 1013(3)

C(37)-P(1)-Pd(1) 1142(2)

C(25)-P(1)-Pd(1) 1091(2)

C(31)-P(1)-Pd(1) 1205(2)

C(43)-P(2)-C(49) 1115(3)

C(43)-P(2)-C(55) 1047(3)

C(49)-P(2)-C(55) 1020(3)

C(43)-P(2)-Pd(1) 1110(2)

C(49)-P(2)-Pd(1) 1132(2)

C(55)-P(2)-Pd(1) 1139(2)

C(61)-P(3)-C(67) 1067(4)

C(61)-P(3)-C(73) 1028(4)

C(67)-P(3)-C(73) 1047(4)

C(61)-P(3)-Pd(2) 1087(3)

C(67)-P(3)-Pd(2) 1122(3)

C(73)-P(3)-Pd(2) 1207(2)

C(85)-P(4)-C(79) 1107(3)

C(85)-P(4)-C(91) 1023(3)

C(79)-P(4)-C(91) 1052(3)

C(85)-P(4)-Pd(2) 1139(3)

C(74)-C(73)-P(3) 1202(6)

C(75)-C(74)-C(73) 1202(8)

C(76)-C(75)-C(74) 1199(7)

C(75)-C(76)-C(77) 1207(8)

C(78)-C(77)-C(76) 1186(9)

C(77)-C(78)-C(73) 1220(7)

C(84)-C(79)-C(80) 1205(6)

C(84)-C(79)-P(4) 1249(5)

C(80)-C(79)-P(4) 1146(5)

C(81)-C(80)-C(79) 1181(7)

C(82)-C(81)-C(80) 1211(7)

C(81)-C(82)-C(83) 1197(7)

C(84)-C(83)-C(82) 1203(7)

C(79)-C(84)-C(83) 1201(7)

C(90)-C(85)-C(86) 1198(7)

C(90)-C(85)-P(4) 1219(6)

C(86)-C(85)-P(4) 1183(6)

C(87)-C(86)-C(85) 1201(8)

C(88)-C(87)-C(86) 1198(8)

C(89)-C(88)-C(87) 1195(7)

C(88)-C(89)-C(90) 1212(9)

C(85)-C(90)-C(89) 1195(8)

C(92)-C(91)-C(96) 1197(6)

C(92)-C(91)-P(4) 1225(5)

C(96)-C(91)-P(4) 1177(5)

C(91)-C(92)-C(93) 1198(7)

C(94)-C(93)-C(92) 1209(7)

C(93)-C(94)-C(95) 1189(7)

C(96)-C(95)-C(94) 1207(7)

C(95)-C(96)-C(91) 1201(6)

F(11)-P(10)-F(15) 920(4)

F(11)-P(10)-F(13) 909(4)

F(15)-P(10)-F(13) 1769(4)

F(11)-P(10)-F(14) 909(4)

F(15)-P(10)-F(14) 889(3)

F(13)-P(10)-F(14) 921(4)

F(11)-P(10)-F(12) 902(4)

F(15)-P(10)-F(12) 897(3)

F(13)-P(10)-F(12) 892(3)

F(14)-P(10)-F(12) 1783(3)

F(11)-P(10)-F(16) 1792(4)

F(15)-P(10)-F(16) 885(4)

F(13)-P(10)-F(16) 885(4)

F(14)-P(10)-F(16) 897(4)

F(12)-P(10)-F(16) 892(3)

F(26)-P(20)-F(21) 1790(6)

F(26)-P(20)-F(25) 893(5)

F(21)-P(20)-F(25) 897(5)

F(26)-P(20)-F(22) 932(6)

F(21)-P(20)-F(22) 865(6)

F(25)-P(20)-F(22) 894(4)

F(26)-P(20)-F(24) 875(6)

F(21)-P(20)-F(24) 928(6)

F(25)-P(20)-F(24) 907(3)

F(22)-P(20)-F(24) 1794(6)

F(26)-P(20)-F(23) 889(4)

F(21)-P(20)-F(23) 921(4)

F(25)-P(20)-F(23) 1780(5)

F(22)-P(20)-F(23) 899(3)

F(24)-P(20)-F(23) 901(3)

223





224




05(C H2 Cl2)






b = 192506(5) Aring = 970520(16)deg

c = 494978(9) Aring = 90deg




F(000) 8880
















225


Pd(1A)-P(2A) 23045(9)

Pd(1A)-P(1A) 23091(9)

Pd(1A)-S(1A) 23294(9)

Pd(1A)-S(3A) 23458(9)

P(1A)-C(22A) 1817(3)

P(1A)-C(28A) 1820(3)

P(1A)-C(16A) 1821(3)

P(1A)-C(22) 1838(8)

P(2A)-C(46A) 1815(4)

P(2A)-C(34A) 1823(4)

P(2A)-C(40A) 1837(4)

P(2A)-C(40) 1843(6)

S(1A)-C(2A) 1726(3)

C(2A)-N(4A) 1306(4)

C(2A)-S(3A) 1717(4)

N(4A)-C(5A) 1467(5)

N(4A)-C(15A) 1467(4)

C(5A)-C(6A) 1528(5)

C(6A)-C(7A) 1512(5)

C(7A)-Si(8A) 1718(5)

C(7A)-Si(8) 2004(6)

Si(8A)-O(13A) 1602(5)

Si(8A)-O(9A) 1629(6)

Si(8A)-O(11A) 1634(5)

O(9A)-C(10A) 1436(8)

O(11A)-C(12A) 1401(8)

O(13A)-C(14A) 1388(9)

Si(8)-O(9) 1606(8)

Si(8)-O(11) 1618(8)

Si(8)-O(13) 1633(8)

O(9)-C(10) 1422(12)

O(11)-C(12) 1418(13)

O(13)-C(14) 1462(12)

C(16A)-C(21A) 1387(5)

C(16A)-C(17A) 1391(5)

C(17A)-C(18A) 1379(5)

C(18A)-C(19A) 1378(6)

C(19A)-C(20A) 1359(6)

C(20A)-C(21A) 1395(5)

C(22A)-C(23A) 13900

C(22A)-C(27A) 13900

C(23A)-C(24A) 13900

C(24A)-C(25A) 13900

C(25A)-C(26A) 13900

C(26A)-C(27A) 13900

C(22)-C(23) 13900

C(22)-C(27) 13900

C(23)-C(24) 13900

C(24)-C(25) 13900

C(25)-C(26) 13900

C(26)-C(27) 13900

C(28A)-C(33A) 1385(5)

C(28A)-C(29A) 1395(5)

C(29A)-C(30A) 1377(5)

C(30A)-C(31A) 1367(6)

C(31A)-C(32A) 1380(6)

C(32A)-C(33A) 1387(5)

C(34A)-C(35A) 1377(5)

C(34A)-C(39A) 1394(5)

O(13)-Si(8)-C(7A) 1101(4)

C(10)-O(9)-Si(8) 1212(8)

C(12)-O(11)-Si(8) 1233(9)

C(14)-O(13)-Si(8) 1224(8)

C(21A)-C(16A)-C(17A) 1189(3)

C(21A)-C(16A)-P(1A) 1232(3)

C(17A)-C(16A)-P(1A) 1178(3)

C(18A)-C(17A)-C(16A) 1206(4)

C(19A)-C(18A)-C(17A) 1198(4)

C(20A)-C(19A)-C(18A) 1205(4)

C(19A)-C(20A)-C(21A) 1203(4)

C(16A)-C(21A)-C(20A) 1198(4)

C(23A)-C(22A)-C(27A) 1200

C(23A)-C(22A)-P(1A) 1187(3)

C(27A)-C(22A)-P(1A) 1213(3)

C(24A)-C(23A)-C(22A) 1200

C(25A)-C(24A)-C(23A) 1200

C(24A)-C(25A)-C(26A) 1200

C(27A)-C(26A)-C(25A) 1200

C(26A)-C(27A)-C(22A) 1200

C(23)-C(22)-C(27) 1200

C(23)-C(22)-P(1A) 1215(7)

C(27)-C(22)-P(1A) 1185(7)

C(24)-C(23)-C(22) 1200

C(25)-C(24)-C(23) 1200

C(24)-C(25)-C(26) 1200

C(25)-C(26)-C(27) 1200

C(26)-C(27)-C(22) 1200

C(33A)-C(28A)-C(29A) 1187(3)

C(33A)-C(28A)-P(1A) 1220(3)

C(29A)-C(28A)-P(1A) 1193(3)

C(30A)-C(29A)-C(28A) 1205(4)

C(31A)-C(30A)-C(29A) 1205(4)

C(30A)-C(31A)-C(32A) 1199(4)

C(31A)-C(32A)-C(33A) 1202(4)

C(28A)-C(33A)-C(32A) 1202(4)

C(35A)-C(34A)-C(39A) 1196(3)

C(35A)-C(34A)-P(2A) 1178(3)

C(39A)-C(34A)-P(2A) 1226(3)

C(34A)-C(35A)-C(36A) 1199(4)

C(37A)-C(36A)-C(35A) 1198(5)

C(38A)-C(37A)-C(36A) 1203(4)

C(37A)-C(38A)-C(39A) 1204(4)

C(38A)-C(39A)-C(34A) 1200(4)

C(41A)-C(40A)-C(45A) 1200

C(41A)-C(40A)-P(2A) 1219(4)

C(45A)-C(40A)-P(2A) 1181(4)

C(42A)-C(41A)-C(40A) 1200

C(41A)-C(42A)-C(43A) 1200

C(42A)-C(43A)-C(44A) 1200

C(45A)-C(44A)-C(43A) 1200

C(44A)-C(45A)-C(40A) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2A) 1242(5)

C(45)-C(40)-P(2A) 1152(6)

C(40)-C(41)-C(42) 1200

C(43)-C(42)-C(41) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

226

C(35A)-C(36A) 1394(6)

C(36A)-C(37A) 1377(7)

C(37A)-C(38A) 1369(7)

C(38A)-C(39A) 1374(5)

C(40A)-C(41A) 13900

C(40A)-C(45A) 13900

C(41A)-C(42A) 13900

C(42A)-C(43A) 13900

C(43A)-C(44A) 13900

C(44A)-C(45A) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46A)-C(51A) 1374(5)

C(46A)-C(47A) 1390(5)

C(47A)-C(48A) 1378(5)

C(48A)-C(49A) 1366(6)

C(49A)-C(50A) 1372(6)

C(50A)-C(51A) 1397(5)

Pd(1B)-P(2B) 22980(9)

Pd(1B)-P(1B) 23261(9)

Pd(1B)-S(1B) 23293(9)

Pd(1B)-S(3B) 23476(10)

P(1B)-C(28) 1800(6)

P(1B)-C(22B) 1817(3)

P(1B)-C(16B) 1822(3)

P(1B)-C(28B) 1853(3)

P(2B)-C(46B) 1725(3)

P(2B)-C(40) 1811(7)

P(2B)-C(34B) 1819(4)

P(2B)-C(40B) 1849(4)

P(2B)-C(46) 1911(5)

S(1B)-C(2B) 1719(4)

C(2B)-N(4B) 1312(5)

C(2B)-S(3B) 1722(4)

N(4B)-C(15B) 1434(7)

N(4B)-C(5) 1434(11)

N(4B)-C(5B) 1523(9)

N(4B)-C(15) 1553(9)

C(5B)-C(6B) 1527(11)

C(6B)-C(7B) 1513(9)

C(7B)-Si(8B) 1842(7)

Si(8B)-O(11B) 1612(6)

Si(8B)-O(9B) 1626(8)

Si(8B)-O(13B) 1629(5)

O(9B)-C(10B) 1426(12)

O(11B)-C(12B) 1431(10)

O(13B)-C(14B) 1383(10)

C(5)-C(6) 1496(12)

C(6)-C(7) 1488(10)

C(7)-Si(8) 1861(8)

Si(8)-O(9) 1577(9)

Si(8)-O(13) 1600(8)

Si(8)-O(11) 1640(8)

O(9)-C(10) 1372(13)

O(11)-C(12) 1411(10)

O(13)-C(14) 1388(12)

C(16B)-C(17B) 1369(5)

C(44)-C(45)-C(40) 1200

C(51A)-C(46A)-C(47A) 1192(3)

C(51A)-C(46A)-P(2A) 1215(3)

C(47A)-C(46A)-P(2A) 1194(3)

C(48A)-C(47A)-C(46A) 1205(4)

C(49A)-C(48A)-C(47A) 1200(4)

C(48A)-C(49A)-C(50A) 1203(4)

C(49A)-C(50A)-C(51A) 1200(4)

C(46A)-C(51A)-C(50A) 1200(4)

P(2B)-Pd(1B)-P(1B) 9991(3)

P(2B)-Pd(1B)-S(1B) 9282(3)

P(1B)-Pd(1B)-S(1B) 16611(3)

P(2B)-Pd(1B)-S(3B) 16751(4)

P(1B)-Pd(1B)-S(3B) 9257(3)

S(1B)-Pd(1B)-S(3B) 7472(4)

C(28)-P(1B)-C(22B) 1115(3)

C(28)-P(1B)-C(16B) 1024(4)

C(22B)-P(1B)-C(16B) 10549(16)

C(22B)-P(1B)-C(28B) 1015(2)

C(16B)-P(1B)-C(28B) 1044(2)

C(28)-P(1B)-Pd(1B) 1174(3)

C(22B)-P(1B)-Pd(1B) 10938(12)

C(16B)-P(1B)-Pd(1B) 10984(12)

C(28B)-P(1B)-Pd(1B) 1245(2)

C(46B)-P(2B)-C(34B) 1031(2)

C(40)-P(2B)-C(34B) 1057(4)

C(46B)-P(2B)-C(40B) 1035(3)

C(34B)-P(2B)-C(40B) 1050(2)

C(40)-P(2B)-C(46) 994(5)

C(34B)-P(2B)-C(46) 1146(3)

C(46B)-P(2B)-Pd(1B) 12210(18)

C(40)-P(2B)-Pd(1B) 1163(4)

C(34B)-P(2B)-Pd(1B) 11240(13)

C(40B)-P(2B)-Pd(1B) 1092(3)

C(46)-P(2B)-Pd(1B) 10795(19)

C(2B)-S(1B)-Pd(1B) 8727(14)

N(4B)-C(2B)-S(1B) 1242(3)

N(4B)-C(2B)-S(3B) 1247(3)

S(1B)-C(2B)-S(3B) 1111(2)

C(2B)-S(3B)-Pd(1B) 8661(13)

C(2B)-N(4B)-C(15B) 1252(5)

C(2B)-N(4B)-C(5) 1241(9)

C(2B)-N(4B)-C(5B) 1207(6)

C(15B)-N(4B)-C(5B) 1135(6)

C(2B)-N(4B)-C(15) 1156(5)

C(5)-N(4B)-C(15) 1200(9)

N(4B)-C(5B)-C(6B) 1098(7)

C(7B)-C(6B)-C(5B) 1152(7)

C(6B)-C(7B)-Si(8B) 1124(5)

O(11B)-Si(8B)-O(9B) 1112(4)

O(11B)-Si(8B)-O(13B) 1081(3)

O(9B)-Si(8B)-O(13B) 1049(4)

O(11B)-Si(8B)-C(7B) 1091(3)

O(9B)-Si(8B)-C(7B) 1110(4)

O(13B)-Si(8B)-C(7B) 1124(3)

C(10B)-O(9B)-Si(8B) 1228(7)

C(12B)-O(11B)-Si(8B) 1249(6)

C(14B)-O(13B)-Si(8B) 1273(7)

N(4B)-C(5)-C(6) 1110(10)

C(7)-C(6)-C(5) 1143(10)

C(6)-C(7)-Si(8) 1165(7)

227

C(16B)-C(21B) 1378(5)

C(17B)-C(18B) 1386(5)

C(18B)-C(19B) 1359(6)

C(19B)-C(20B) 1360(6)

C(20B)-C(21B) 1384(5)

C(22B)-C(23B) 1383(5)

C(22B)-C(27B) 1385(5)

C(23B)-C(24B) 1384(6)

C(24B)-C(25B) 1362(7)

C(25B)-C(26B) 1364(7)

C(26B)-C(27B) 1373(5)

C(28B)-C(29B) 13900

C(28B)-C(33B) 13900

C(29B)-C(30B) 13900

C(30B)-C(31B) 13900

C(31B)-C(32B) 13900

C(32B)-C(33B) 13900

C(28)-C(29) 13900

C(28)-C(33) 13900

C(29)-C(30) 13900

C(30)-C(31) 13900

C(31)-C(32) 13900

C(32)-C(33) 13900

C(34B)-C(35B) 1381(6)

C(34B)-C(39B) 1396(6)

C(35B)-C(36B) 1394(6)

C(36B)-C(37B) 1388(7)

C(37B)-C(38B) 1363(8)

C(38B)-C(39B) 1383(7)

C(40B)-C(41B) 13900

C(40B)-C(45B) 13900

C(41B)-C(42B) 13900

C(42B)-C(43B) 13900

C(43B)-C(44B) 13900

C(44B)-C(45B) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46B)-C(47B) 13900

C(46B)-C(51B) 13900

C(47B)-C(48B) 13900

C(48B)-C(49B) 13900

C(49B)-C(50B) 13900

C(50B)-C(51B) 13900

C(46)-C(47) 13900

C(46)-C(51) 13900

C(47)-C(48) 13900

C(48)-C(49) 13900

C(49)-C(50) 13900

C(50)-C(51) 13900

P(60)-F(65) 1563(4)

P(60)-F(62) 1570(4)

P(60)-F(64) 1572(4)

P(60)-F(63) 1581(4)

P(60)-F(66) 1592(4)

P(60)-F(61) 1601(4)

P(60)-F(62) 1557(11)

P(60)-F(64) 1562(11)

O(9)-Si(8)-O(13) 1091(6)

O(9)-Si(8)-O(11) 1115(5)

O(13)-Si(8)-O(11) 1066(4)

O(9)-Si(8)-C(7) 1042(6)

O(13)-Si(8)-C(7) 1119(4)

O(11)-Si(8)-C(7) 1135(4)

C(10)-O(9)-Si(8) 1269(9)

C(12)-O(11)-Si(8) 1245(7)

C(14)-O(13)-Si(8) 1277(8)

C(17B)-C(16B)-C(21B) 1181(3)

C(17B)-C(16B)-P(1B) 1190(3)

C(21B)-C(16B)-P(1B) 1229(3)

C(16B)-C(17B)-C(18B) 1213(4)

C(19B)-C(18B)-C(17B) 1199(4)

C(18B)-C(19B)-C(20B) 1197(4)

C(19B)-C(20B)-C(21B) 1206(4)

C(16B)-C(21B)-C(20B) 1204(4)

C(23B)-C(22B)-C(27B) 1181(3)

C(23B)-C(22B)-P(1B) 1225(3)

C(27B)-C(22B)-P(1B) 1194(3)

C(22B)-C(23B)-C(24B) 1204(4)

C(25B)-C(24B)-C(23B) 1204(4)

C(24B)-C(25B)-C(26B) 1198(4)

C(25B)-C(26B)-C(27B) 1203(4)

C(26B)-C(27B)-C(22B) 1209(4)

C(29B)-C(28B)-C(33B) 1200

C(29B)-C(28B)-P(1B) 1201(3)

C(33B)-C(28B)-P(1B) 1199(3)

C(28B)-C(29B)-C(30B) 1200

C(31B)-C(30B)-C(29B) 1200

C(30B)-C(31B)-C(32B) 1200

C(31B)-C(32B)-C(33B) 1200

C(32B)-C(33B)-C(28B) 1200

C(29)-C(28)-C(33) 1200

C(29)-C(28)-P(1B) 1209(5)

C(33)-C(28)-P(1B) 1190(5)

C(30)-C(29)-C(28) 1200

C(29)-C(30)-C(31) 1200

C(30)-C(31)-C(32) 1200

C(33)-C(32)-C(31) 1200

C(32)-C(33)-C(28) 1200

C(35B)-C(34B)-C(39B) 1196(4)

C(35B)-C(34B)-P(2B) 1173(3)

C(39B)-C(34B)-P(2B) 1230(4)

C(34B)-C(35B)-C(36B) 1205(4)

C(37B)-C(36B)-C(35B) 1192(5)

C(38B)-C(37B)-C(36B) 1202(5)

C(37B)-C(38B)-C(39B) 1213(5)

C(38B)-C(39B)-C(34B) 1191(5)

C(41B)-C(40B)-C(45B) 1200

C(41B)-C(40B)-P(2B) 1245(4)

C(45B)-C(40B)-P(2B) 1153(4)

C(40B)-C(41B)-C(42B) 1200

C(43B)-C(42B)-C(41B) 1200

C(44B)-C(43B)-C(42B) 1200

C(43B)-C(44B)-C(45B) 1200

C(44B)-C(45B)-C(40B) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2B) 1183(7)

C(45)-C(40)-P(2B) 1217(7)

C(42)-C(41)-C(40) 1200

228

P(60)-F(63) 1568(11)

P(60)-F(65) 1571(11)

P(60)-F(61) 1585(11)

P(60)-F(66) 1605(11)

P(70)-F(73) 1564(3)

P(70)-F(71) 1570(3)

P(70)-F(74) 1570(3)

P(70)-F(75) 1577(3)

P(70)-F(72) 1586(3)

P(70)-F(76) 1592(3)

C(80)-Cl(82) 1647(11)

C(80)-Cl(81) 1747(11)

C(90)-Cl(92) 165(5)

C(90)-Cl(91) 185(7)

P(2A)-Pd(1A)-P(1A) 10199(3)

P(2A)-Pd(1A)-S(1A) 9315(3)

P(1A)-Pd(1A)-S(1A) 16444(3)

P(2A)-Pd(1A)-S(3A) 16753(3)

P(1A)-Pd(1A)-S(3A) 8973(3)

S(1A)-Pd(1A)-S(3A) 7492(3)

C(22A)-P(1A)-C(28A) 1062(2)

C(22A)-P(1A)-C(16A) 1044(2)

C(28A)-P(1A)-C(16A) 10468(16)

C(28A)-P(1A)-C(22) 960(5)

C(16A)-P(1A)-C(22) 1101(5)

C(22A)-P(1A)-Pd(1A) 10918(18)

C(28A)-P(1A)-Pd(1A) 12376(11)

C(16A)-P(1A)-Pd(1A) 10703(12)

C(22)-P(1A)-Pd(1A) 1144(4)

C(46A)-P(2A)-C(34A) 10586(16)

C(46A)-P(2A)-C(40A) 989(3)

C(34A)-P(2A)-C(40A) 1086(3)

C(46A)-P(2A)-C(40) 1060(4)

C(34A)-P(2A)-C(40) 1032(4)

C(46A)-P(2A)-Pd(1A) 11826(12)

C(34A)-P(2A)-Pd(1A) 11366(12)

C(40A)-P(2A)-Pd(1A) 1103(3)

C(40)-P(2A)-Pd(1A) 1086(4)

C(2A)-S(1A)-Pd(1A) 8685(13)

N(4A)-C(2A)-S(3A) 1252(3)

N(4A)-C(2A)-S(1A) 1234(3)

S(3A)-C(2A)-S(1A) 1114(2)

C(2A)-S(3A)-Pd(1A) 8652(12)

C(2A)-N(4A)-C(5A) 1217(3)

C(2A)-N(4A)-C(15A) 1220(3)

C(5A)-N(4A)-C(15A) 1162(3)

N(4A)-C(5A)-C(6A) 1100(3)

C(7A)-C(6A)-C(5A) 1121(3)

C(6A)-C(7A)-Si(8A) 1149(3)

C(6A)-C(7A)-Si(8) 1142(3)

O(13A)-Si(8A)-O(9A) 1067(3)

O(13A)-Si(8A)-O(11A) 1115(3)

O(9A)-Si(8A)-O(11A) 1063(3)

O(13A)-Si(8A)-C(7A) 1115(3)

O(9A)-Si(8A)-C(7A) 1113(3)

O(11A)-Si(8A)-C(7A) 1093(3)

C(10A)-O(9A)-Si(8A) 1226(5)

C(12A)-O(11A)-Si(8A) 1220(5)

C(14A)-O(13A)-Si(8A) 1221(6)

O(9)-Si(8)-O(11) 1128(5)

C(41)-C(42)-C(43) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

C(44)-C(45)-C(40) 1200

C(47B)-C(46B)-C(51B) 1200

C(47B)-C(46B)-P(2B) 1224(3)

C(51B)-C(46B)-P(2B) 1176(3)

C(46B)-C(47B)-C(48B) 1200

C(47B)-C(48B)-C(49B) 1200

C(50B)-C(49B)-C(48B) 1200

C(49B)-C(50B)-C(51B) 1200

C(50B)-C(51B)-C(46B) 1200

C(47)-C(46)-C(51) 1200

C(47)-C(46)-P(2B) 1201(3)

C(51)-C(46)-P(2B) 1199(3)

C(48)-C(47)-C(46) 1200

C(49)-C(48)-C(47) 1200

C(50)-C(49)-C(48) 1200

C(49)-C(50)-C(51) 1200

C(50)-C(51)-C(46) 1200

F(65)-P(60)-F(62) 921(3)

F(65)-P(60)-F(64) 890(3)

F(62)-P(60)-F(64) 1789(4)

F(65)-P(60)-F(63) 1788(3)

F(62)-P(60)-F(63) 887(3)

F(64)-P(60)-F(63) 902(3)

F(65)-P(60)-F(66) 899(3)

F(62)-P(60)-F(66) 900(3)

F(64)-P(60)-F(66) 903(3)

F(63)-P(60)-F(66) 910(3)

F(65)-P(60)-F(61) 901(3)

F(62)-P(60)-F(61) 893(3)

F(64)-P(60)-F(61) 903(3)

F(63)-P(60)-F(61) 890(3)

F(66)-P(60)-F(61) 1793(4)

F(62)-P(60)-F(64) 1789(9)

F(62)-P(60)-F(63) 890(7)

F(64)-P(60)-F(63) 910(7)

F(62)-P(60)-F(65) 896(7)

F(64)-P(60)-F(65) 904(7)

F(63)-P(60)-F(65) 1783(9)

F(62)-P(60)-F(61) 904(7)

F(64)-P(60)-F(61) 907(7)

F(63)-P(60)-F(61) 901(7)

F(65)-P(60)-F(61) 909(7)

F(62)-P(60)-F(66) 901(7)

F(64)-P(60)-F(66) 888(7)

F(63)-P(60)-F(66) 893(7)

F(65)-P(60)-F(66) 897(7)

F(61)-P(60)-F(66) 1792(10)

F(73)-P(70)-F(71) 910(2)

F(73)-P(70)-F(74) 912(2)

F(71)-P(70)-F(74) 8971(19)

F(73)-P(70)-F(75) 1774(2)

F(71)-P(70)-F(75) 8995(18)

F(74)-P(70)-F(75) 913(2)

F(73)-P(70)-F(72) 898(2)

F(71)-P(70)-F(72) 9080(18)

F(74)-P(70)-F(72) 1789(2)

F(75)-P(70)-F(72) 8775(19)

F(73)-P(70)-F(76) 8966(18)

229

O(9)-Si(8)-O(13) 1017(5)

O(11)-Si(8)-O(13) 1130(5)

O(9)-Si(8)-C(7A) 1118(5)

O(11)-Si(8)-C(7A) 1074(4)

F(71)-P(70)-F(76) 1790(2)

F(74)-P(70)-F(76) 8954(17)

F(75)-P(70)-F(76) 8944(18)

F(72)-P(70)-F(76) 8994(17)

Cl(82)-C(80)-Cl(81) 1144(7)

Cl(92)-C(90)-Cl(91) 1077(16)











230

b = 147655(6) Aring = 76579(4)deg

c = 162359(7) Aring = 81131(3)deg




F(000) 1228

















Pd(1)-P(2) 22919(8)

Pd(1)-P(1) 23209(8)

Pd(1)-S(1) 23312(8)

Pd(1)-S(3) 23603(8)

P(1)-C(37) 1818(3)

P(1)-C(31) 1820(4)

P(1)-C(25) 1823(4)

P(2)-C(43) 1813(4)

P(2)-C(55) 1820(4)

P(2)-C(49) 1834(3)

S(1)-C(2) 1724(4)

C(2)-N(4) 1310(5)

C(2)-S(3) 1724(3)

N(4)-C(15) 1475(5)

N(4)-C(5) 1483(5)

C(5)-C(6) 1505(6)

C(6)-C(7) 1489(7)

C(7)-Si(8) 1873(5)

Si(8)-O(11) 1496(7)

Si(8)-O(13) 1557(11)

Si(8)-O(9) 1565(12)

Si(8)-O(9) 1624(6)

Si(8)-O(13) 1633(5)

S(3)-C(2)-S(1) 11213(19)

C(2)-S(3)-Pd(1) 8590(12)

C(2)-N(4)-C(15) 1217(3)

C(2)-N(4)-C(5) 1206(3)

C(15)-N(4)-C(5) 1177(3)

N(4)-C(5)-C(6) 1148(4)

C(7)-C(6)-C(5) 1142(4)

C(6)-C(7)-Si(8) 1144(3)

O(13)-Si(8)-O(9) 1104(10)

O(11)-Si(8)-O(9) 1059(5)

O(11)-Si(8)-O(13) 1110(3)

O(9)-Si(8)-O(13) 1031(4)

O(13)-Si(8)-O(11) 1029(7)

O(9)-Si(8)-O(11) 1063(8)

O(11)-Si(8)-C(7) 1136(3)

O(13)-Si(8)-C(7) 1206(7)

O(9)-Si(8)-C(7) 1088(12)

O(9)-Si(8)-C(7) 1139(6)

O(13)-Si(8)-C(7) 1089(3)

O(11)-Si(8)-C(7) 1069(7)

C(10)-O(9)-Si(8) 1278(8)

C(12)-O(11)-Si(8) 1307(7)

C(14)-O(13)-Si(8) 1264(7)

231

Si(8)-O(11) 1664(11)

O(9)-C(10) 1395(9)

O(11)-C(12) 1457(8)

O(13)-C(14) 1401(9)

O(9)-C(10) 1410(13)

O(11)-C(12) 1438(14)

O(13)-C(14) 1399(14)

C(15)-C(16) 1517(5)

C(16)-C(17) 1540(6)

C(17)-Si(18) 1853(5)

Si(18)-O(19) 1609(4)

Si(18)-O(21) 1614(4)

Si(18)-O(23) 1620(13)

Si(18)-O(23) 1636(5)

Si(18)-O(19) 1649(13)

Si(18)-O(21) 1658(14)

O(19)-C(20) 1413(8)

O(21)-C(22) 1370(9)

O(23)-C(24) 1359(9)

O(19)-C(20) 1398(16)

O(21)-C(22) 1396(17)

O(23)-C(24) 1392(16)

C(25)-C(26) 1393(5)

C(25)-C(30) 1399(5)

C(26)-C(27) 1388(6)

C(27)-C(28) 1372(7)

C(28)-C(29) 1376(7)

C(29)-C(30) 1395(6)

C(31)-C(32) 1388(5)

C(31)-C(36) 1397(5)

C(32)-C(33) 1389(5)

C(33)-C(34) 1383(6)

C(34)-C(35) 1391(5)

C(35)-C(36) 1383(5)

C(37)-C(38) 1395(5)

C(37)-C(42) 1397(5)

C(38)-C(39) 1382(5)

C(39)-C(40) 1393(6)

C(40)-C(41) 1380(6)

C(41)-C(42) 1383(5)

C(43)-C(44) 1387(5)

C(43)-C(48) 1399(5)

C(44)-C(45) 1393(5)

C(45)-C(46) 1383(6)

C(46)-C(47) 1383(6)

C(47)-C(48) 1389(5)

C(49)-C(50) 1384(5)

C(49)-C(54) 1404(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1377(7)

C(52)-C(53) 1384(7)

C(53)-C(54) 1394(5)

C(55)-C(60) 1391(5)

C(55)-C(56) 1394(5)

C(56)-C(57) 1384(6)

C(57)-C(58) 1386(7)

C(58)-C(59) 1382(7)

C(59)-C(60) 1392(6)

P(3)-F(6) 1588(3)

P(3)-F(5) 1590(3)

P(3)-F(3) 1591(3)

C(10)-O(9)-Si(8) 1321(16)

C(12)-O(11)-Si(8) 1203(13)

C(14)-O(13)-Si(8) 1323(16)

N(4)-C(15)-C(16) 1126(3)

C(15)-C(16)-C(17) 1103(3)

C(16)-C(17)-Si(18) 1159(3)

O(19)-Si(18)-O(21) 1125(4)

O(19)-Si(18)-O(23) 1106(3)

O(21)-Si(18)-O(23) 1077(3)

O(23)-Si(18)-O(19) 1101(10)

O(23)-Si(18)-O(21) 1067(11)

O(19)-Si(18)-O(21) 1059(10)

O(19)-Si(18)-C(17) 1084(2)

O(21)-Si(18)-C(17) 1107(4)

O(23)-Si(18)-C(17) 1215(11)

O(23)-Si(18)-C(17) 1068(3)

O(19)-Si(18)-C(17) 1003(9)

O(21)-Si(18)-C(17) 1112(16)

C(20)-O(19)-Si(18) 1270(6)

C(22)-O(21)-Si(18) 1283(6)

C(24)-O(23)-Si(18) 1306(7)

C(20)-O(19)-Si(18) 1250(17)

C(22)-O(21)-Si(18) 1231(18)

C(24)-O(23)-Si(18) 1266(19)

C(26)-C(25)-C(30) 1189(4)

C(26)-C(25)-P(1) 1195(3)

C(30)-C(25)-P(1) 1215(3)

C(27)-C(26)-C(25) 1204(4)

C(28)-C(27)-C(26) 1209(4)

C(27)-C(28)-C(29) 1191(4)

C(28)-C(29)-C(30) 1215(4)

C(29)-C(30)-C(25) 1192(4)

C(32)-C(31)-C(36) 1202(3)

C(32)-C(31)-P(1) 1202(3)

C(36)-C(31)-P(1) 1195(3)

C(31)-C(32)-C(33) 1193(3)

C(34)-C(33)-C(32) 1206(3)

C(33)-C(34)-C(35) 1201(3)

C(36)-C(35)-C(34) 1198(3)

C(35)-C(36)-C(31) 1201(3)

C(38)-C(37)-C(42) 1186(3)

C(38)-C(37)-P(1) 1181(3)

C(42)-C(37)-P(1) 1233(3)

C(39)-C(38)-C(37) 1207(3)

C(38)-C(39)-C(40) 1204(4)

C(41)-C(40)-C(39) 1189(4)

C(40)-C(41)-C(42) 1212(4)

C(41)-C(42)-C(37) 1201(4)

C(44)-C(43)-C(48) 1197(3)

C(44)-C(43)-P(2) 1250(3)

C(48)-C(43)-P(2) 1153(3)

C(43)-C(44)-C(45) 1194(4)

C(46)-C(45)-C(44) 1208(4)

C(45)-C(46)-C(47) 1200(4)

C(46)-C(47)-C(48) 1198(4)

C(47)-C(48)-C(43) 1203(4)

C(50)-C(49)-C(54) 1194(3)

C(50)-C(49)-P(2) 1226(3)

C(54)-C(49)-P(2) 1179(3)

C(49)-C(50)-C(51) 1203(4)

C(52)-C(51)-C(50) 1201(4)

232

P(3)-F(4) 1591(3)

P(3)-F(1) 1591(3)

P(3)-F(2) 1606(3)

P(2)-Pd(1)-P(1) 9913(3)

P(2)-Pd(1)-S(1) 9341(3)

P(1)-Pd(1)-S(1) 16715(3)

P(2)-Pd(1)-S(3) 16839(3)

P(1)-Pd(1)-S(3) 9221(3)

S(1)-Pd(1)-S(3) 7514(3)

C(37)-P(1)-C(31) 10350(15)

C(37)-P(1)-C(25) 10696(16)

C(31)-P(1)-C(25) 10397(16)

C(37)-P(1)-Pd(1) 12280(11)

C(31)-P(1)-Pd(1) 11250(11)

C(25)-P(1)-Pd(1) 10556(11)

C(43)-P(2)-C(55) 11078(16)

C(43)-P(2)-C(49) 10469(16)

C(55)-P(2)-C(49) 10265(16)

C(43)-P(2)-Pd(1) 10997(12)

C(55)-P(2)-Pd(1) 11546(12)

C(49)-P(2)-Pd(1) 11259(11)

C(2)-S(1)-Pd(1) 8681(12)

N(4)-C(2)-S(3) 1239(3)

N(4)-C(2)-S(1) 1239(3)

C(51)-C(52)-C(53) 1203(4)

C(52)-C(53)-C(54) 1200(4)

C(53)-C(54)-C(49) 1198(4)

C(60)-C(55)-C(56) 1195(3)

C(60)-C(55)-P(2) 1194(3)

C(56)-C(55)-P(2) 1210(3)

C(57)-C(56)-C(55) 1198(4)

C(56)-C(57)-C(58) 1207(4)

C(59)-C(58)-C(57) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(55)-C(60)-C(59) 1202(4)

F(6)-P(3)-F(5) 8938(18)

F(6)-P(3)-F(3) 9022(16)

F(5)-P(3)-F(3) 1796(2)

F(6)-P(3)-F(4) 9002(16)

F(5)-P(3)-F(4) 9024(18)

F(3)-P(3)-F(4) 8977(16)

F(6)-P(3)-F(1) 17916(19)

F(5)-P(3)-F(1) 913(2)

F(3)-P(3)-F(1) 8906(18)

F(4)-P(3)-F(1) 904(2)

F(6)-P(3)-F(2) 8873(16)

F(5)-P(3)-F(2) 9101(19)

F(3)-P(3)-F(2) 8896(16)

F(4)-P(3)-F(2) 1782(2)

F(1)-P(3)-F(2) 908(2)

233



example)

iii




















iv

Publications








v

Acknowledgements













they are missing








vi












vii

Abstract




























viii










ix

Abbreviations






x

Contents

Declaration ii


Publication iv

Acknowledgement v

Abstract vii

Abbreviations ix

Contents x



1





6












xi

16 References 31






45


51







25 Conclusion 66

26 References 67





73


73



79



xii



84


87




90


35 Conclusion 96

36 References 98





102





112



118




121

45 Conclusion 128

46 References 130

xiii





133




136


(37) 138









148


149


152

55 Conclusion 154

56 References 156


61 Conclusions 158

62 Future work 159

xiv





731 KS2CN(CH2py)2 (1) 163

732 [Au(S2CN(CH2py)2)(PPh3)] (2) 163

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3) 164





738 [Ni(S2C-N(CH2py)2)] (8) 166







170


170


7317 (SC6H4CO2H-4)2 (17) 172

7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18) 172



173


174

xv






741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 178

742 [Pd(S2CNEt2)2] (24) 178



(26) 179

745 [Pd(Me2dazdt)2]I6 (27) 180

746 [PdI2(Me2dazdt)] (28) 180

747 [Pd(Cy2DTO)2]I8 (29) 180



751 (TBA)2[Pd2I6] (30) 186

752 Trans-PdI2(PPh3)2 (31) 186

753 [PdI2(dppe)] (32) 187

754 [PdI2(dppf)] (33) 187







xvi




195


195


196


8 Appendices



201



204



(22)

208



212



216


219



223



223


229



1

























2











(Figure 112)8




3




















4
























5













6














7




















8























9












catalysis









10






























carbon (C-C) bond

11















C)42


12





















metals


13









mechanisms















14



















15

















16














(80)56











17


















18


















19



























20


























21




















22














23












of product92







24
















25






















0

500

1000

1500

2000

2500

1992 1997 2003 2008 2014

Pri

ce (

USD

pe

r O

z)

Year

Pt

Pd

26





















27



























PGMs112






28



concerns114


















143

29


15 Thesis overview










also investigated



30











31

16 References
























32

37 2466ndash2468

























33























70 Chem Abs 1969 71 114951




34
























35























36


37

























(Figure 211)


38
















manner













39
















mz 200











40




at mz 274


41


































42


































43














44

































45




ligand










Figure 231












46













47






















formulation










48

















complexes
















49















50
































51





nitrogen)

























52


















53





























54




















55


































56




















8764(18)deg]37


57































58


















59
















(Figure 245)








60










NP1 (Figure 246)








61




















0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

(

)

Temperature ()

62


















63







0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

64



















65



0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

66

25 Conclusion















67

26 References





















68























69









70































71

























72

















catalystsrdquo19












73































74
















75






















76









77











Pt(PPh3)2

27

2354(1) 2355(1)

1318 (6)

1723(5) 1725(5)

1118(3)

7467 (4)

Pd(dppf)27

23370(1) 2358(1)

1322(6)

1725(5) 1735(5)

1121(3)

7518(5)

Pd(PPh3)2 (25-A)

23304(10) 23536(10)

1302(5)

1722(4) 1735(4)

1112(2)

7504(4)

Pd(PPh3)2 (25-B)

23388 (8) 23479(9)

1326(4)

1714(4) 1727(4)

11276(19)

7536(3)





(Figure 324)

78












Pd(dppf)26

23348(6) 23516(6) 23347(6) 23445(7)

1313(3) 1323(3)

1728(2) 1719(2) 1709(2) 1723(2)

11188(14) 11215(13)

7507(2) 7498(2)

Pd(PPh3)2 (26)

23720(16) 23190(15) 23735(17) 23180(15

1323(8) 1316(9)

1715(7) 1718(6) 1722(7) 1727(7)

1132(4) 1119(4)

7528(5) 7505(5)

79























80
















81















A

Me MeOH 12 22 95

Et EtOH 51 24 80



B Me MeOH 19 18 80

82



reaction























block and vials





83



























byproducts

84








impact


(SOCDTC)







86

75

8784

87

69

8784

0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Perc

enta

ge y

ield

(

)


22hr 2hr

85


time


















30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Pd loading (mol)

86



















0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Yie

ld

)

Catalyst


87































88










(h)

Yield

()

SD

A

Et

23 2 89 (20)

24 2 83 (10)

25 2 64 (21)

26 2 65 (35)

Pri

23 8 90 (14)

24 24 99 (00)

25 4 97 (12)

26 8 91 (25)

CH2CF3

23 4 92 (10)

24 4 99 (00)

25 2 99 (06)

26 2 95 (17)

B

Me

23 2 66 (02)

24 6 40 (02)

25 2 78 (02)

26 2 46 (44)






89





























90



(mol)

Temperature

(degC)

Time

(h)

Yield

()

A

Me

Me

27 1 100

100

2 87

Pd(OAc)2 1 22 95

Me 27 1 50 2 67

Me Pd(OAc)2 1 50 2 33


catalysts (SOCDTO)










0

20

40

60

80

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

1 mol 2 mol

91


















0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Time (hours)

1 mol 2 mol

92



(mol)

Time

(h)

Yield

()

SD

()

1

1 39 05

A

Pri

27

2 48 06

3 52 07

4 52 09

5 53 08

Pri

27

2

1 74 31

2 79 23

3 81 27

4 83 27

5 83 30

A

CF3CH2

27

2

1 49 05

2 72 09

3 85 11

4 92 00

5 96 05






or 2 hours

93


T = 50 degC








89

9899 99

85

92

9596

75

80

85

90

95

100

105

1 2 3 4

Yie

ld (

)

Time (hours)


40

50

60

70

80

90

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

EtOH iPrOH

94













0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10

Yie

ld (

)

Time (hours)


95







(mol)

Time

(h)

Yield

()

SD

()

2

1 53 11

B

OMe

28

2 95 05

3 100 05

4 100 00

5 100 00

B

OMe

29

2

1 54 20

2 89 08

3 99 02

4 100 00

5 100 00











96




method (100)

35 Conclusion



























97









98

36 References




















99











100






























101













and Singulair56

















102






















secondary source







103
















104























105













above11













sections






106

























107









A

1 mol

Me 2 94 ( 02)

Et 2 43 ( 02)

Pri 2 52 ( 47)

CH2CF3 2 93 ( 30)

2 mol

Me 2 99 ( 04)

EtOH 2 81 ( 33)

Pri 2 75 ( 40)

CH2CF3 2 99 ( 15)













108






















original work

109













50

MeOH

11 Pd

1 34

2 39

5 73

22 87

100

MeOH

11 Pd

1 91

2 90

5 92

22 92







A MeOH 11 22 95

110




















111








nm17

















112






catalyst
















113








0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25

Yiel

d (

)

Time (hours)


114

















0

20

40

60

80

100

120

0 5 10 15 20 25 30

Yiel

d (

)

Time (hours)


115













B Me 1 mol 2 80 (02)

2 mol 2 87 (16)







116





















B

MeOH

1 mol

2 96 ( 02)

4 94 ( 17)

6 96 ( 03)

24 95 (12)

B

MeOH

2 mol

2 99 (06)

4 99 (04)

6 99 (04)

24 99 (05)



117







C AcOH 1 mol 2 61 ( 30)

2 mol 2 83 ( 40)













C

AcOH

1 mol

2 44 ( 28)

4 55 ( 06)

6 62 ( 25)

24 71 ( 16)

C

AcOH

2 mol

2 71 ( 78)

4 71 ( 21)

6 72 ( 13)

24 85 ( 38)

118


















119




























120









coupling reaction



















reading

121













coupling reactions












122


Catalyst Pd

loadings

(mol )

Yield ()


[PdI2(PPh3)2] (31)

05



























123

















coupling reactions




80

85

90

95

100

105


Yiel

d (

)

Catalysts

30 min 60 min

124















K2CO3 in ethanol











125




















80

85

90

95

100

30 60 90

Yie

ld (

)

Time (min)

(TBA)₂[Pd₂I₆] (30) [PdCl₂(PPh₃)₂]

126

















0

10

20

30

40

50

60

70

80

90

100

90 120 150

Pro

du

ct y

ield

(

)

Time (min)


127




60 968 plusmn 04


60 973 plusmn 15


60 996 plusmn 01


60 995 plusmn 01









0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


128










45 Conclusion











0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


129




excellent yield










130

46 References























131
























132
































133














oxidant PhI(OAc)2











134






















135
















products










both complexes







136
















137












138



25-A

23304(10)

23536(10)

1302(5)

1722(4)

1735(4)

1112(2)

7504(4)

36-A

23294(9)

23458(9)

1306(4)

1726(3)

1717(4)

1114(2)

7492(3)

36-B

23293(9)

23476(10)

1312(5)

1719(4)

1722(4)

1111(2)

7472(3)








C(10)-O(9)-Si(8) 1226˚ (5) 1228˚ (7) 02˚

C(12)-O(11)-Si(8) 1220˚ (5) 1249˚ (6) 29˚

C(14)-O(13)-Si(8) 1221˚ (6) 1273˚ (7) 52˚







139











140













Reaction

Catalyst Pd

(mol)

Temperature

(degC)

Time

(h)

Yield

()

SD

A

36

1

100

2

85 ( 06)

37 85 ( 07)

23 87 (10)

141











product








0

10

20

30

40

50

60

70

1 2 3 4 5 6

Yiel

d (

)

Time (hours)

36 37

142



















0

20

40

60

80

100

120

0 1 2 3 4 5 6

Yiel

d (

)


36 37

143









(h)

Yield

()

SD

Et

23 2 89 (20)

A

36 24 99 (04)

37 24 42 (34)

CH2CF3

23 4 92 (10)

36 6 98 (02)

37 6 90 (17)

B Me 23 2 66 (02)

37 6 60 (38)















144





magnetic field14















145






















146



nanoparticles















147



















ethanol and dried









148







and dried















149








complexes













physisorbed

150











nanoparticles


151






















60

65

70

75

80

85

90

95

100

0 100 200 300 400 500 600

Weig

ht (

)

Temperature ()


152



palladium catalyst










h)








153



36SiO2Fe3O4 32 13 5 -

36SiO2Fe3O4 32 27 10 6



























154









55 Conclusion






















155






156

56 References























157










158


61 Conclusions



















donor groups










159

















system

62 Future work













160



161

7 Experimental





























162


























163


731 KS2CN(CH2py)2 (1)








mg (84) IR 2923 (νC-H) 2361 1591 1570 1474 1434 (νC-N) 1358 1302 1183





(100) [M-K]ˉ

732 [Au(S2CN(CH2py)2)(PPh3)] (2)












N 56

164

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3)














37 Found C 497 H 37 N 35















C 585 H 44 N 34

165




















677 H 48 N 41











166









45 N 35











1915 (νCO) 1589 1570 1475 1432 1409 1207 1157 1090 1001 750 689 cmndash1





37 Found C 699 H 47 N 37

738 [Ni(S2C-N(CH2py)2)] (8)




167









H 40 N 138 Found C 433 H 36 N 108




















199616) C 641 H 45 N 14 Found C 637 H 42 N 18

168



















H 43 N 16













169







H 42 N 10












715 H 51 N 10











170











(CO) 1890 (CO) 1531 (OCO) 1481 1433 1391 1184 1090 979 827 743 692 cmndash












= 208951) C 615 H 41 N 13 Found C 614 H 39 N 14








171








226170) C 643 H 39 N 12 Found C 641 H 38 N 12



















C 509 H 33 N 13

172

7317 (SC6H4CO2H-4)2 (17)






2669 2552 1676 (VCO) 1591 1423 1323 1292 1181 1116 933 850 cmndash1 1H NMR



7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18)





















H 42 Found C 586 H 42

173































174









= 138224) C 617 H 42 Found C 617 H 41


















175






1535 1481 1434 1419 1176 1095 862 744 692 cm-1 1H NMR (CD2Cl2) 578 (d







H 33 N 16 Found C 526 H 34 N 17



















176














x 2 2 x 2H PCH2P) 661 (m 4H C6H5) 710 726 738 754 772 794 (m x 6 36H


















177





178


741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 925













742 [Pd(S2CNEt2)2] (24)26













179






(79) IR (ATR) 1514 1480 1434 1280 1239 1094 999 (νC-S) 831 (νPF) cm-1 1H






524 H 38 N 16 Found C 525 H 37 N 16




















180


745 [Pd(Me2dazdt)2]I6 (27)







1429 1393 1357 1330 1287 1283 1107 1073 1028 981 825 743610 581 532


NCH2 JHH = 67 Hz)









1527 1460 1423 1395 1359 1330 1286 1264 1223 1114 1073 1027 958 897



literature28

747 [Pd(Cy2DTO)2]I8 (29)





181







199 H 29 N 33 Found C 203 H 28 N 34
















data

182





183

























184












method data (99)





Hz 20 Hz) 726 (dd 1H J = 80 Hz 10 Hz) 419 (s3H)





3H J = 70 Hz)




60 Hz) 150 (t 6H J = 60 Hz)



185






3H)

186


751 (TBA)2[Pd2I6]30 (30)


























187

753 [PdI2(dppe)] (32)





Yield 325 mg (87) IR 3052 1437 1100 998 877 811 701 688 678 cm-1 1H




754 [PdI2(dppf)] (33)






= 242 (s dppf) ppm







188












step












189






















190






by 1H NMR




746 (dd 1H JHH = 786 Hz 42 Hz) 586 (s2H) 216 (s 3H)











isolated yield

191



















192



















C 310 H 60 N 45












193






H 66 N 31 Found C 341 H 67 N 32



















47 N 14






194





























195






(129 g)














603 563 (νFeO) cm-1









196

SiO236 NP



SiO236 NP











36SiO2Fe3O4


588 (νFeO) cm-1


37SiO2Fe3O4



197










catalyst system





NMR



198

References




















199






















200

2013 49 11358ndash60

201

Appendices



N(CH2py)2)(CO)(PPh3)2] (5)









b = 148523(7) Aring = 82606(3)deg

c = 179728(7) Aring = 87478(3)deg




202

F(000) 1164

















Ru(1)-C(28) 1836(3)

Ru(1)-C(19) 2083(3)

Ru(1)-P(2) 23706(8)

Ru(1)-P(1) 23823(8)

Ru(1)-S(3) 24740(8)

Ru(1)-S(1) 25025(8)

P(1)-C(29) 1834(3)

P(1)-C(35) 1834(3)

P(1)-C(41) 1845(4)

P(2)-C(53) 1827(3)

P(2)-C(59) 1837(3)

P(2)-C(47) 1845(3)

S(1)-C(2) 1715(3)

C(2)-N(4) 1333(4)

C(2)-S(3) 1698(3)

N(4)-C(5) 1457(5)

N(4)-C(12) 1461(4)

C(5)-C(6) 1516(5)

C(6)-N(7) 1344(5)

C(6)-C(11) 1372(5)

N(7)-C(8) 1353(6)

C(8)-C(9) 1382(7)

C(9)-C(10) 1366(7)

C(10)-C(11) 1368(6)

C(12)-C(13) 1519(6)

C(13)-N(14) 1335(5)

C(13)-C(18) 1370(6)

N(14)-C(15) 1360(7)

C(15)-C(16) 1339(9)

C(16)-C(17) 1354(8)

C(17)-C(18) 1398(7)

C(29)-P(1)-Ru(1) 11804(10)

C(35)-P(1)-Ru(1) 11715(11)

C(41)-P(1)-Ru(1) 11341(12)

C(53)-P(2)-C(59) 10292(15)

C(53)-P(2)-C(47) 10443(14)

C(59)-P(2)-C(47) 9991(14)

C(53)-P(2)-Ru(1) 11295(10)

C(59)-P(2)-Ru(1) 11877(11)

C(47)-P(2)-Ru(1) 11586(11)

C(2)-S(1)-Ru(1) 8783(12)

N(4)-C(2)-S(3) 1241(3)

N(4)-C(2)-S(1) 1227(3)

S(3)-C(2)-S(1) 11319(18)

C(2)-S(3)-Ru(1) 8915(11)

C(2)-N(4)-C(5) 1221(3)

C(2)-N(4)-C(12) 1210(3)

C(5)-N(4)-C(12) 1168(3)

N(4)-C(5)-C(6) 1153(3)

N(7)-C(6)-C(11) 1231(4)

N(7)-C(6)-C(5) 1139(3)

C(11)-C(6)-C(5) 1230(3)

C(6)-N(7)-C(8) 1168(4)

N(7)-C(8)-C(9) 1230(4)

C(10)-C(9)-C(8) 1182(4)

C(9)-C(10)-C(11) 1201(4)

C(10)-C(11)-C(6) 1187(4)

N(4)-C(12)-C(13) 1144(3)

N(14)-C(13)-C(18) 1227(4)

N(14)-C(13)-C(12) 1133(4)

C(18)-C(13)-C(12) 1240(3)

C(13)-N(14)-C(15) 1159(5)

203

C(19)-C(20) 1333(5)

C(20)-C(21) 1477(5)

C(21)-C(22) 1395(5)

C(21)-C(26) 1403(5)

C(22)-C(23) 1388(5)

C(23)-C(24) 1386(6)

C(24)-C(25) 1384(6)

C(24)-C(27) 1519(6)

C(25)-C(26) 1386(5)

C(28)-O(28) 1138(4)

C(29)-C(34) 1388(5)

C(29)-C(30) 1397(5)

C(30)-C(31) 1383(5)

C(31)-C(32) 1387(6)

C(32)-C(33) 1378(6)

C(33)-C(34) 1396(5)

C(35)-C(36) 1373(6)

C(35)-C(40) 1393(5)

C(36)-C(37) 1382(5)

C(37)-C(38) 1380(6)

C(38)-C(39) 1359(7)

C(39)-C(40) 1404(5)

C(41)-C(42) 1383(6)

C(41)-C(46) 1393(5)

C(42)-C(43) 1389(7)

C(43)-C(44) 1372(9)

C(44)-C(45) 1371(8)

C(45)-C(46) 1392(6)

C(47)-C(52) 1386(4)

C(47)-C(48) 1393(5)

C(48)-C(49) 1384(5)

C(49)-C(50) 1384(5)

C(50)-C(51) 1381(6)

C(51)-C(52) 1396(5)

C(53)-C(58) 1388(5)

C(53)-C(54) 1393(5)

C(54)-C(55) 1407(5)

C(55)-C(56) 1375(6)

C(56)-C(57) 1384(6)

C(57)-C(58) 1393(5)

C(59)-C(64) 1384(5)

C(59)-C(60) 1395(5)

C(60)-C(61) 1394(5)

C(61)-C(62) 1381(7)

C(62)-C(63) 1378(7)

C(63)-C(64) 1399(5)

C(28)-Ru(1)-C(19) 9900(14)

C(28)-Ru(1)-P(2) 9001(10)

C(19)-Ru(1)-P(2) 8442(9)

C(28)-Ru(1)-P(1) 8661(11)

C(19)-Ru(1)-P(1) 8546(9)

P(2)-Ru(1)-P(1) 16869(3)

C(28)-Ru(1)-S(3) 16962(11)

C(19)-Ru(1)-S(3) 9137(9)

P(2)-Ru(1)-S(3) 9142(3)

P(1)-Ru(1)-S(3) 9385(3)

C(28)-Ru(1)-S(1) 9981(11)

C(19)-Ru(1)-S(1) 16110(9)

P(2)-Ru(1)-S(1) 9381(3)

P(1)-Ru(1)-S(1) 9739(3)

C(16)-C(15)-N(14) 1249(5)

C(15)-C(16)-C(17) 1188(5)

C(16)-C(17)-C(18) 1187(5)

C(13)-C(18)-C(17) 1190(4)

C(20)-C(19)-Ru(1) 1263(2)

C(19)-C(20)-C(21) 1261(3)

C(22)-C(21)-C(26) 1174(3)

C(22)-C(21)-C(20) 1231(3)

C(26)-C(21)-C(20) 1195(3)

C(23)-C(22)-C(21) 1211(3)

C(24)-C(23)-C(22) 1212(4)

C(25)-C(24)-C(23) 1181(4)

C(25)-C(24)-C(27) 1218(4)

C(23)-C(24)-C(27) 1202(4)

C(24)-C(25)-C(26) 1213(3)

C(25)-C(26)-C(21) 1210(3)

O(28)-C(28)-Ru(1) 1776(3)

C(34)-C(29)-C(30) 1192(3)

C(34)-C(29)-P(1) 1224(3)

C(30)-C(29)-P(1) 1183(3)

C(31)-C(30)-C(29) 1202(3)

C(30)-C(31)-C(32) 1204(3)

C(33)-C(32)-C(31) 1196(3)

C(32)-C(33)-C(34) 1204(4)

C(29)-C(34)-C(33) 1201(3)

C(36)-C(35)-C(40) 1179(3)

C(36)-C(35)-P(1) 1208(3)

C(40)-C(35)-P(1) 1214(3)

C(35)-C(36)-C(37) 1214(4)

C(38)-C(37)-C(36) 1208(5)

C(39)-C(38)-C(37) 1187(4)

C(38)-C(39)-C(40) 1210(4)

C(35)-C(40)-C(39) 1202(4)

C(42)-C(41)-C(46) 1184(4)

C(42)-C(41)-P(1) 1223(3)

C(46)-C(41)-P(1) 1193(3)

C(41)-C(42)-C(43) 1208(5)

C(44)-C(43)-C(42) 1201(5)

C(45)-C(44)-C(43) 1201(4)

C(44)-C(45)-C(46) 1201(4)

C(45)-C(46)-C(41) 1205(4)

C(52)-C(47)-C(48) 1186(3)

C(52)-C(47)-P(2) 1223(3)

C(48)-C(47)-P(2) 1189(2)

C(49)-C(48)-C(47) 1207(3)

C(50)-C(49)-C(48) 1203(4)

C(51)-C(50)-C(49) 1196(3)

C(50)-C(51)-C(52) 1200(3)

C(47)-C(52)-C(51) 1207(3)

C(58)-C(53)-C(54) 1197(3)

C(58)-C(53)-P(2) 1197(2)

C(54)-C(53)-P(2) 1199(3)

C(53)-C(54)-C(55) 1196(3)

C(56)-C(55)-C(54) 1201(3)

C(55)-C(56)-C(57) 1204(3)

C(56)-C(57)-C(58) 1200(4)

C(53)-C(58)-C(57) 1203(3)

C(64)-C(59)-C(60) 1194(3)

C(64)-C(59)-P(2) 1210(3)

C(60)-C(59)-P(2) 1196(3)

C(61)-C(60)-C(59) 1201(4)

204

S(3)-Ru(1)-S(1) 6983(3)

C(29)-P(1)-C(35) 10221(15)

C(29)-P(1)-C(41) 10252(17)

C(35)-P(1)-C(41) 10111(16)

C(62)-C(61)-C(60) 1199(4)

C(63)-C(62)-C(61) 1205(4)

C(62)-C(63)-C(64) 1198(4)

C(59)-C(64)-C(63) 1204(4)





5(C H2 Cl2)






b = 217537(9) Aring = 92572(4)deg

c = 304002(14) Aring = 90deg

205




F(000) 3136

















Ru(1)-O(3) 2161(4)

Ru(1)-O(1) 2232(4)

Ru(1)-P(43) 22640(16)

Ru(1)-P(13) 22916(17)

Ru(1)-P(11) 23361(16)

Ru(1)-P(41) 23570(16)

Ru(1)-C(2) 2531(6)

O(1)-C(2) 1267(7)

C(2)-O(3) 1260(7)

C(2)-C(4) 1489(8)

C(4)-C(9) 1370(9)

C(4)-C(5) 1380(8)

C(5)-C(6) 1387(8)

C(6)-N(7) 1333(8)

C(6)-C(6)1 1475(12)

N(7)-C(8) 1338(9)

C(8)-C(9) 1390(9)

P(11)-C(20) 1806(6)

P(11)-C(14) 1818(6)

P(11)-C(12) 1829(6)

C(12)-P(13) 1854(6)

P(13)-C(26) 1815(6)

P(13)-C(32) 1820(6)

C(14)-C(15) 1371(9)

C(14)-C(19) 1395(8)

C(15)-C(16) 1395(9)

C(16)-C(17) 1373(10)

C(5)-C(6)-C(6)1 1212(7)

C(6)-N(7)-C(8) 1175(6)

N(7)-C(8)-C(9) 1236(6)

C(4)-C(9)-C(8) 1180(6)

C(20)-P(11)-C(14) 1050(3)

C(20)-P(11)-C(12) 1088(3)

C(14)-P(11)-C(12) 1074(3)

C(20)-P(11)-Ru(1) 1157(2)

C(14)-P(11)-Ru(1) 1235(2)

C(12)-P(11)-Ru(1) 950(2)

P(11)-C(12)-P(13) 948(3)

C(26)-P(13)-C(32) 1043(3)

C(26)-P(13)-C(12) 1024(3)

C(32)-P(13)-C(12) 1072(3)

C(26)-P(13)-Ru(1) 1188(2)

C(32)-P(13)-Ru(1) 1249(2)

C(12)-P(13)-Ru(1) 958(2)

C(15)-C(14)-C(19) 1200(6)

C(15)-C(14)-P(11) 1205(5)

C(19)-C(14)-P(11) 1194(5)

C(14)-C(15)-C(16) 1200(6)

C(17)-C(16)-C(15) 1194(7)

C(18)-C(17)-C(16) 1208(7)

C(17)-C(18)-C(19) 1202(7)

C(18)-C(19)-C(14) 1195(7)

C(25)-C(20)-C(21) 1195(6)

C(25)-C(20)-P(11) 1227(5)

206

C(17)-C(18) 1370(11)

C(18)-C(19) 1377(9)

C(20)-C(25) 1371(9)

C(20)-C(21) 1395(9)

C(21)-C(22) 1370(10)

C(22)-C(23) 1375(12)

C(23)-C(24) 1383(13)

C(24)-C(25) 1397(11)

C(26)-C(31) 1375(9)

C(26)-C(27) 1402(8)

C(27)-C(28) 1383(9)

C(28)-C(29) 1361(10)

C(29)-C(30) 1388(10)

C(30)-C(31) 1384(10)

C(32)-C(37) 1378(9)

C(32)-C(33) 1412(9)

C(33)-C(34) 1376(10)

C(34)-C(35) 1354(11)

C(35)-C(36) 1381(11)

C(36)-C(37) 1385(9)

P(41)-C(50) 1818(6)

P(41)-C(44) 1823(7)

P(41)-C(42) 1851(6)

C(42)-P(43) 1849(6)

P(43)-C(62) 1811(6)

P(43)-C(56) 1829(7)

C(44)-C(49) 1384(9)

C(44)-C(45) 1387(9)

C(45)-C(46) 1383(10)

C(46)-C(47) 1377(12)

C(47)-C(48) 1386(12)

C(48)-C(49) 1366(11)

C(50)-C(55) 1375(9)

C(50)-C(51) 1398(9)

C(51)-C(52) 1386(9)

C(52)-C(53) 1364(11)

C(53)-C(54) 1385(11)

C(54)-C(55) 1382(10)

C(56)-C(57) 1357(9)

C(56)-C(61) 1388(9)

C(57)-C(58) 1392(10)

C(58)-C(59) 1376(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1380(10)

C(62)-C(63) 1386(9)

C(62)-C(67) 1395(8)

C(63)-C(64) 1396(9)

C(64)-C(65) 1362(10)

C(65)-C(66) 1370(10)

C(66)-C(67) 1385(8)

B(70)-C(83) 1628(11)

B(70)-C(77) 1635(11)

B(70)-C(89) 1644(11)

B(70)-C(71) 1659(10)

C(71)-C(76) 1367(10)

C(71)-C(72) 1398(10)

C(72)-C(73) 1367(11)

C(73)-C(74) 1346(13)

C(74)-C(75) 1370(13)

C(75)-C(76) 1403(11)

C(77)-C(82) 1376(10)

C(21)-C(20)-P(11) 1172(5)

C(22)-C(21)-C(20) 1209(7)

C(21)-C(22)-C(23) 1193(8)

C(22)-C(23)-C(24) 1211(8)

C(23)-C(24)-C(25) 1191(8)

C(20)-C(25)-C(24) 1201(7)

C(31)-C(26)-C(27) 1182(6)

C(31)-C(26)-P(13) 1203(5)

C(27)-C(26)-P(13) 1207(5)

C(28)-C(27)-C(26) 1201(6)

C(29)-C(28)-C(27) 1208(6)

C(28)-C(29)-C(30) 1201(7)

C(31)-C(30)-C(29) 1192(7)

C(26)-C(31)-C(30) 1217(7)

C(37)-C(32)-C(33) 1184(6)

C(37)-C(32)-P(13) 1193(5)

C(33)-C(32)-P(13) 1221(5)

C(34)-C(33)-C(32) 1195(7)

C(35)-C(34)-C(33) 1215(7)

C(34)-C(35)-C(36) 1199(7)

C(35)-C(36)-C(37) 1199(8)

C(32)-C(37)-C(36) 1208(7)

C(50)-P(41)-C(44) 1009(3)

C(50)-P(41)-C(42) 1075(3)

C(44)-P(41)-C(42) 1055(3)

C(50)-P(41)-Ru(1) 1224(2)

C(44)-P(41)-Ru(1) 1243(2)

C(42)-P(41)-Ru(1) 9385(19)

P(43)-C(42)-P(41) 952(3)

C(62)-P(43)-C(56) 1029(3)

C(62)-P(43)-C(42) 1067(3)

C(56)-P(43)-C(42) 1063(3)

C(62)-P(43)-Ru(1) 1294(2)

C(56)-P(43)-Ru(1) 1125(2)

C(42)-P(43)-Ru(1) 970(2)

C(49)-C(44)-C(45) 1201(7)

C(49)-C(44)-P(41) 1214(5)

C(45)-C(44)-P(41) 1185(5)

C(46)-C(45)-C(44) 1188(7)

C(47)-C(46)-C(45) 1211(8)

C(46)-C(47)-C(48) 1195(8)

C(49)-C(48)-C(47) 1200(8)

C(48)-C(49)-C(44) 1206(7)

C(55)-C(50)-C(51) 1187(6)

C(55)-C(50)-P(41) 1226(5)

C(51)-C(50)-P(41) 1185(5)

C(52)-C(51)-C(50) 1195(6)

C(53)-C(52)-C(51) 1208(7)

C(52)-C(53)-C(54) 1203(7)

C(55)-C(54)-C(53) 1188(7)

C(50)-C(55)-C(54) 1218(7)

C(57)-C(56)-C(61) 1194(6)

C(57)-C(56)-P(43) 1190(5)

C(61)-C(56)-P(43) 1214(5)

C(56)-C(57)-C(58) 1204(7)

C(59)-C(58)-C(57) 1206(7)

C(60)-C(59)-C(58) 1184(7)

C(59)-C(60)-C(61) 1214(7)

C(60)-C(61)-C(56) 1197(7)

C(63)-C(62)-C(67) 1188(6)

C(63)-C(62)-P(43) 1211(5)

207

C(77)-C(78) 1406(11)

C(78)-C(79) 1390(11)

C(79)-C(80) 1367(12)

C(80)-C(81) 1350(13)

C(81)-C(82) 1412(12)

C(83)-C(88) 1388(11)

C(83)-C(84) 1410(11)

C(84)-C(85) 1398(12)

C(85)-C(86) 1379(14)

C(86)-C(87) 1372(14)

C(87)-C(88) 1399(12)

C(89)-C(94) 1392(10)

C(89)-C(90) 1412(10)

C(90)-C(91) 1387(11)

C(91)-C(92) 1365(13)

C(92)-C(93) 1353(12)

C(93)-C(94) 1402(11)

C(100)-Cl(2) 1707(11)

C(100)-Cl(1) 1727(11)

C(110)-Cl(4) 1639(14)

C(110)-Cl(3) 1720(12)

C(120)-Cl(5) 1670(15)

C(120)-Cl(6) 1751(16)

O(3)-Ru(1)-O(1) 5979(15)

O(3)-Ru(1)-P(43) 9947(12)

O(1)-Ru(1)-P(43) 15664(11)

O(3)-Ru(1)-P(13) 16018(12)

O(1)-Ru(1)-P(13) 10841(11)

P(43)-Ru(1)-P(13) 9445(6)

O(3)-Ru(1)-P(11) 9159(12)

O(1)-Ru(1)-P(11) 9023(11)

P(43)-Ru(1)-P(11) 10176(6)

P(13)-Ru(1)-P(11) 7170(6)

O(3)-Ru(1)-P(41) 9644(12)

O(1)-Ru(1)-P(41) 9776(11)

P(43)-Ru(1)-P(41) 7245(6)

P(13)-Ru(1)-P(41) 10118(6)

P(11)-Ru(1)-P(41) 17076(6)

O(3)-Ru(1)-C(2) 2985(16)

O(1)-Ru(1)-C(2) 3003(16)

P(43)-Ru(1)-C(2) 12894(14)

P(13)-Ru(1)-C(2) 13584(14)

P(11)-Ru(1)-C(2) 8942(13)

P(41)-Ru(1)-C(2) 9982(13)

C(2)-O(1)-Ru(1) 882(3)

O(3)-C(2)-O(1) 1201(5)

O(3)-C(2)-C(4) 1191(5)

O(1)-C(2)-C(4) 1208(5)

O(3)-C(2)-Ru(1) 586(3)

O(1)-C(2)-Ru(1) 618(3)

C(4)-C(2)-Ru(1) 1735(4)

C(2)-O(3)-Ru(1) 916(4)

C(67)-C(62)-P(43) 1201(5)

C(62)-C(63)-C(64) 1199(6)

C(65)-C(64)-C(63) 1203(7)

C(64)-C(65)-C(66) 1207(6)

C(65)-C(66)-C(67) 1197(6)

C(66)-C(67)-C(62) 1206(6)

C(83)-B(70)-C(77) 1137(6)

C(83)-B(70)-C(89) 1124(6)

C(77)-B(70)-C(89) 1039(6)

C(83)-B(70)-C(71) 1032(6)

C(77)-B(70)-C(71) 1114(6)

C(89)-B(70)-C(71) 1124(6)

C(76)-C(71)-C(72) 1146(7)

C(76)-C(71)-B(70) 1245(7)

C(72)-C(71)-B(70) 1209(7)

C(73)-C(72)-C(71) 1239(8)

C(74)-C(73)-C(72) 1201(9)

C(73)-C(74)-C(75) 1188(8)

C(74)-C(75)-C(76) 1206(9)

C(71)-C(76)-C(75) 1219(8)

C(82)-C(77)-C(78) 1150(7)

C(82)-C(77)-B(70) 1238(7)

C(78)-C(77)-B(70) 1208(7)

C(79)-C(78)-C(77) 1230(8)

C(80)-C(79)-C(78) 1199(9)

C(81)-C(80)-C(79) 1191(9)

C(80)-C(81)-C(82) 1211(8)

C(77)-C(82)-C(81) 1220(8)

C(88)-C(83)-C(84) 1154(8)

C(88)-C(83)-B(70) 1249(8)

C(84)-C(83)-B(70) 1196(8)

C(85)-C(84)-C(83) 1222(10)

C(86)-C(85)-C(84) 1197(10)

C(87)-C(86)-C(85) 1201(10)

C(86)-C(87)-C(88) 1194(11)

C(83)-C(88)-C(87) 1232(10)

C(94)-C(89)-C(90) 1145(7)

C(94)-C(89)-B(70) 1249(6)

C(90)-C(89)-B(70) 1204(7)

C(91)-C(90)-C(89) 1227(8)

C(92)-C(91)-C(90) 1202(8)

C(93)-C(92)-C(91) 1196(9)

C(92)-C(93)-C(94) 1206(8)

C(89)-C(94)-C(93) 1224(8)

Cl(2)-C(100)-Cl(1) 1150(7)

Cl(4)-C(110)-Cl(3) 1199(8)

Cl(5)-C(120)-Cl(6) 1119(9)

208





25(C H2 Cl2)






b = 147789(5) Aring = 73377(3)deg

c = 214417(6) Aring = 75105(3)deg




F(000) 1926







209











Au(1)-P(11) 22545(16)

Au(1)-S(10) 23027(16)

Re(1)-C(83) 1895(7)

Re(1)-C(84) 1915(7)

Re(1)-C(85) 1931(9)

Re(1)-C(85) 1947(7)

Re(1)-N(43) 2161(5)

Re(1)-N(32) 2175(5)

Re(1)-Cl(1) 2271(8)

Re(1)-Cl(1) 2337(4)

Ru(1)-C(82) 1807(6)

Ru(1)-C(30) 2013(5)

Ru(1)-O(1) 2194(3)

Ru(1)-O(3) 2236(4)

Ru(1)-P(63) 23781(16)

Ru(1)-P(44) 23806(17)

Ru(1)-C(2) 2564(5)

C(85)-O(85) 1187(8)

C(85)-O(85) 1178(9)

O(1)-C(2) 1255(7)

C(2)-O(3) 1268(7)

C(2)-C(4) 1480(7)

C(4)-C(9) 1377(8)

C(4)-C(5) 1399(8)

C(5)-C(6) 1360(8)

C(6)-C(7) 1376(8)

C(7)-C(8) 1376(8)

C(7)-S(10) 1761(6)

C(8)-C(9) 1392(8)

P(11)-C(18) 1800(6)

P(11)-C(24) 1811(6)

P(11)-C(12) 1824(6)

C(12)-C(13) 1386(8)

C(12)-C(17) 1388(9)

C(13)-C(14) 1360(10)

C(14)-C(15) 1383(11)

C(15)-C(16) 1395(10)

C(16)-C(17) 1366(9)

C(18)-C(23) 1374(9)

C(18)-C(19) 1405(9)

C(19)-C(20) 1388(9)

C(20)-C(21) 1378(10)

C(21)-C(22) 1346(11)

C(30)-Ru(1)-C(2) 1308(2)

O(1)-Ru(1)-C(2) 2928(16)

O(3)-Ru(1)-C(2) 2965(16)

P(63)-Ru(1)-C(2) 8971(14)

P(44)-Ru(1)-C(2) 8897(14)

O(85)-C(85)-Re(1) 1747(13)

O(85)-C(85)-Re(1) 176(4)

C(2)-O(1)-Ru(1) 919(3)

O(1)-C(2)-O(3) 1194(5)

O(1)-C(2)-C(4) 1223(5)

O(3)-C(2)-C(4) 1183(5)

O(1)-C(2)-Ru(1) 588(3)

O(3)-C(2)-Ru(1) 607(3)

C(4)-C(2)-Ru(1) 1784(4)

C(2)-O(3)-Ru(1) 897(3)

C(9)-C(4)-C(5) 1186(5)

C(9)-C(4)-C(2) 1207(5)

C(5)-C(4)-C(2) 1207(6)

C(6)-C(5)-C(4) 1199(6)

C(5)-C(6)-C(7) 1226(6)

C(8)-C(7)-C(6) 1176(5)

C(8)-C(7)-S(10) 1237(5)

C(6)-C(7)-S(10) 1187(5)

C(7)-C(8)-C(9) 1212(6)

C(4)-C(9)-C(8) 1202(6)

C(7)-S(10)-Au(1) 1059(2)

C(18)-P(11)-C(24) 1048(3)

C(18)-P(11)-C(12) 1061(3)

C(24)-P(11)-C(12) 1055(3)

C(18)-P(11)-Au(1) 1112(2)

C(24)-P(11)-Au(1) 1164(2)

C(12)-P(11)-Au(1) 1120(2)

C(13)-C(12)-C(17) 1192(6)

C(13)-C(12)-P(11) 1191(5)

C(17)-C(12)-P(11) 1217(5)

C(14)-C(13)-C(12) 1206(7)

C(13)-C(14)-C(15) 1207(7)

C(14)-C(15)-C(16) 1188(6)

C(17)-C(16)-C(15) 1204(7)

C(16)-C(17)-C(12) 1203(7)

C(23)-C(18)-C(19) 1183(6)

C(23)-C(18)-P(11) 1231(5)

C(19)-C(18)-P(11) 1186(5)

210

C(22)-C(23) 1422(10)

C(24)-C(25) 1378(9)

C(24)-C(29) 1384(8)

C(25)-C(26) 1368(9)

C(26)-C(27) 1380(10)

C(27)-C(28) 1370(10)

C(28)-C(29) 1387(9)

C(30)-C(31) 1331(7)

C(31)-C(34) 1456(8)

N(32)-C(33) 1326(7)

N(32)-C(37) 1356(7)

C(33)-C(34) 1390(8)

C(34)-C(35) 1399(8)

C(35)-C(36) 1363(8)

C(36)-C(37) 1384(8)

C(37)-C(38) 1482(8)

C(38)-N(43) 1341(7)

C(38)-C(39) 1372(8)

C(39)-C(40) 1386(9)

C(40)-C(41) 1364(9)

C(41)-C(42) 1371(9)

C(42)-N(43) 1347(8)

P(44)-C(45) 1819(7)

P(44)-C(57) 1820(7)

P(44)-C(51) 1830(4)

P(44)-C(51) 1861(15)

C(45)-C(46) 1379(10)

C(45)-C(50) 1385(10)

C(46)-C(47) 1356(10)

C(47)-C(48) 1331(14)

C(48)-C(49) 1359(13)

C(49)-C(50) 1397(11)

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(57)-C(58) 1390(9)

C(57)-C(62) 1396(9)

C(58)-C(59) 1396(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1366(10)

C(61)-C(62) 1401(9)

P(63)-C(70) 1812(7)

P(63)-C(76) 1817(9)

P(63)-C(76) 1831(5)

P(63)-C(64) 1831(6)

C(64)-C(65) 1367(9)

C(64)-C(69) 1379(8)

C(65)-C(66) 1381(9)

C(66)-C(67) 1352(9)

C(67)-C(68) 1382(10)

C(68)-C(69) 1394(8)

C(70)-C(75) 1371(10)

C(20)-C(19)-C(18) 1209(6)

C(21)-C(20)-C(19) 1208(7)

C(22)-C(21)-C(20) 1184(7)

C(21)-C(22)-C(23) 1227(7)

C(18)-C(23)-C(22) 1189(7)

C(25)-C(24)-C(29) 1188(6)

C(25)-C(24)-P(11) 1219(5)

C(29)-C(24)-P(11) 1190(5)

C(26)-C(25)-C(24) 1212(6)

C(25)-C(26)-C(27) 1195(7)

C(28)-C(27)-C(26) 1206(7)

C(27)-C(28)-C(29) 1194(7)

C(24)-C(29)-C(28) 1205(7)

C(31)-C(30)-Ru(1) 1354(5)

C(30)-C(31)-C(34) 1249(6)

C(33)-N(32)-C(37) 1176(5)

C(33)-N(32)-Re(1) 1254(4)

C(37)-N(32)-Re(1) 1168(4)

N(32)-C(33)-C(34) 1257(6)

C(33)-C(34)-C(35) 1148(5)

C(33)-C(34)-C(31) 1212(5)

C(35)-C(34)-C(31) 1239(5)

C(36)-C(35)-C(34) 1211(6)

C(35)-C(36)-C(37) 1194(6)

N(32)-C(37)-C(36) 1213(5)

N(32)-C(37)-C(38) 1151(5)

C(36)-C(37)-C(38) 1235(5)

N(43)-C(38)-C(39) 1214(6)

N(43)-C(38)-C(37) 1151(5)

C(39)-C(38)-C(37) 1234(6)

C(38)-C(39)-C(40) 1208(6)

C(41)-C(40)-C(39) 1172(6)

C(40)-C(41)-C(42) 1201(6)

N(43)-C(42)-C(41) 1226(6)

C(38)-N(43)-C(42) 1179(5)

C(38)-N(43)-Re(1) 1180(4)

C(42)-N(43)-Re(1) 1241(4)

C(45)-P(44)-C(57) 1029(3)

C(45)-P(44)-C(51) 1036(4)

C(57)-P(44)-C(51) 1002(4)

C(45)-P(44)-C(51) 1043(12)

C(57)-P(44)-C(51) 1099(10)

C(45)-P(44)-Ru(1) 1140(2)

C(57)-P(44)-Ru(1) 1181(2)

C(51)-P(44)-Ru(1) 1160(3)

C(51)-P(44)-Ru(1) 1068(12)

C(46)-C(45)-C(50) 1180(7)

C(46)-C(45)-P(44) 1194(6)

C(50)-C(45)-P(44) 1226(6)

C(47)-C(46)-C(45) 1219(8)

C(48)-C(47)-C(46) 1204(9)

C(47)-C(48)-C(49) 1203(8)

C(48)-C(49)-C(50) 1208(9)

C(45)-C(50)-C(49) 1186(8)

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1173(4)

C(56)-C(51)-P(44) 1227(4)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

211

C(70)-C(71) 1386(9)

C(71)-C(72) 1392(12)

C(72)-C(73) 1341(13)

C(73)-C(74) 1368(13)

C(74)-C(75) 1396(11)

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(82)-O(82) 1152(7)

C(83)-O(83) 1152(7)

C(84)-O(84) 1138(8)

P(11)-Au(1)-S(10) 17634(6)

C(83)-Re(1)-C(84) 865(3)

C(83)-Re(1)-C(85) 861(15)

C(84)-Re(1)-C(85) 924(15)

C(83)-Re(1)-C(85) 896(5)

C(84)-Re(1)-C(85) 887(5)

C(83)-Re(1)-N(43) 1003(2)

C(84)-Re(1)-N(43) 1732(2)

C(85)-Re(1)-N(43) 884(14)

C(85)-Re(1)-N(43) 910(5)

C(83)-Re(1)-N(32) 1743(2)

C(84)-Re(1)-N(32) 986(2)

C(85)-Re(1)-N(32) 913(15)

C(85)-Re(1)-N(32) 930(5)

N(43)-Re(1)-N(32) 7463(18)

C(83)-Re(1)-Cl(1) 974(3)

C(84)-Re(1)-Cl(1) 941(3)

C(85)-Re(1)-Cl(1) 1729(14)

N(43)-Re(1)-Cl(1) 848(2)

N(32)-Re(1)-Cl(1) 847(2)

C(83)-Re(1)-Cl(1) 873(3)

C(84)-Re(1)-Cl(1) 926(3)

C(85)-Re(1)-Cl(1) 1766(5)

N(43)-Re(1)-Cl(1) 8805(17)

N(32)-Re(1)-Cl(1) 8998(17)

C(82)-Ru(1)-C(30) 917(3)

C(82)-Ru(1)-O(1) 1667(2)

C(30)-Ru(1)-O(1) 10156(19)

C(82)-Ru(1)-O(3) 1078(2)

C(30)-Ru(1)-O(3) 1604(2)

O(1)-Ru(1)-O(3) 5893(14)

C(82)-Ru(1)-P(63) 8796(19)

C(30)-Ru(1)-P(63) 9106(17)

O(1)-Ru(1)-P(63) 9197(11)

O(3)-Ru(1)-P(63) 8801(11)

C(82)-Ru(1)-P(44) 9536(19)

C(30)-Ru(1)-P(44) 8717(17)

O(1)-Ru(1)-P(44) 8519(11)

O(3)-Ru(1)-P(44) 9255(11)

P(63)-Ru(1)-P(44) 17628(6)

C(55)-C(56)-C(51) 1200

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1203(18)

C(56)-C(51)-P(44) 1196(18)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

C(55)-C(56)-C(51) 1200

C(58)-C(57)-C(62) 1183(6)

C(58)-C(57)-P(44) 1217(6)

C(62)-C(57)-P(44) 1199(5)

C(57)-C(58)-C(59) 1199(8)

C(60)-C(59)-C(58) 1211(8)

C(61)-C(60)-C(59) 1200(7)

C(60)-C(61)-C(62) 1198(7)

C(57)-C(62)-C(61) 1208(7)

C(70)-P(63)-C(76) 1091(6)

C(70)-P(63)-C(76) 1009(4)

C(70)-P(63)-C(64) 1038(3)

C(76)-P(63)-C(64) 1055(7)

C(76)-P(63)-C(64) 1038(5)

C(70)-P(63)-Ru(1) 1150(2)

C(76)-P(63)-Ru(1) 1081(6)

C(76)-P(63)-Ru(1) 1166(4)

C(64)-P(63)-Ru(1) 11489(19)

C(65)-C(64)-C(69) 1180(6)

C(65)-C(64)-P(63) 1231(4)

C(69)-C(64)-P(63) 1189(5)

C(64)-C(65)-C(66) 1216(6)

C(67)-C(66)-C(65) 1204(7)

C(66)-C(67)-C(68) 1196(6)

C(67)-C(68)-C(69) 1195(6)

C(64)-C(69)-C(68) 1208(7)

C(75)-C(70)-C(71) 1178(7)

C(75)-C(70)-P(63) 1200(5)

C(71)-C(70)-P(63) 1221(6)

C(70)-C(71)-C(72) 1205(8)

C(73)-C(72)-C(71) 1195(8)

C(72)-C(73)-C(74) 1225(9)

C(73)-C(74)-C(75) 1173(10)

C(70)-C(75)-C(74) 1223(8)

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1210(6)

C(81)-C(76)-P(63) 1190(6)

C(76)-C(77)-C(78) 1200

C(79)-C(78)-C(77) 1200

C(78)-C(79)-C(80) 1200

C(81)-C(80)-C(79) 1200

C(80)-C(81)-C(76) 1200

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1215(10)

C(81)-C(76)-P(63) 1184(10)

C(78)-C(77)-C(76) 1200

C(77)-C(78)-C(79) 1200

C(80)-C(79)-C(78) 1200

C(79)-C(80)-C(81) 1200

C(80)-C(81)-C(76) 1200

O(82)-C(82)-Ru(1) 1771(5)

O(83)-C(83)-Re(1) 1771(7)

O(84)-C(84)-Re(1) 1793(6)

212

C(82)-Ru(1)-C(2) 1374(2)










b = 155218(4) Aring = 107289(3)deg

c = 268129(9) Aring = 90deg




F(000) 3784






213












Pd(1)-P(2) 22948(10)

Pd(1)-P(1) 23232(10)

Pd(1)-S(3) 23304(10)

Pd(1)-S(1) 23536(10)

Pd(2)-P(4) 22985(10)

Pd(2)-S(12) 23240(10)

Pd(2)-P(3) 23292(10)

Pd(2)-S(10) 23512(10)

P(1)-C(13) 1814(4)

P(1)-C(25) 1815(4)

P(1)-C(19) 1818(4)

P(2)-C(31) 1809(4)

P(2)-C(43) 1810(4)

P(2)-C(37) 1823(4)

P(3)-C(49) 1805(4)

P(3)-C(61) 1822(4)

P(3)-C(55) 1822(4)

P(4)-C(79) 1818(4)

P(4)-C(67) 1821(4)

P(4)-C(73) 1826(4)

S(1)-C(2) 1735(4)

C(2)-N(4) 1302(5)

C(2)-S(3) 1722(4)

N(4)-C(5) 1458(5)

N(4)-C(9) 1478(5)

C(5)-C(6) 1524(6)

C(6)-N(7) 1473(5)

N(7)-C(11) 1308(5)

N(7)-C(8) 1464(5)

C(8)-C(9) 1511(6)

S(10)-C(11) 1728(4)

C(11)-S(12) 1717(4)

C(13)-C(18) 1380(6)

C(13)-C(14) 1383(6)

C(14)-C(15) 1384(7)

C(15)-C(16) 1371(8)

C(16)-C(17) 1341(8)

C(17)-C(18) 1383(7)

C(19)-C(24) 1371(6)

C(19)-C(20) 1392(6)

C(20)-C(21) 1372(7)

C(79)-P(4)-C(73) 9763(18)

C(67)-P(4)-C(73) 1063(2)

C(79)-P(4)-Pd(2) 11555(13)

C(67)-P(4)-Pd(2) 10862(13)

C(73)-P(4)-Pd(2) 11746(14)

C(2)-S(1)-Pd(1) 8607(13)

N(4)-C(2)-S(3) 1232(3)

N(4)-C(2)-S(1) 1256(3)

S(3)-C(2)-S(1) 1112(2)

C(2)-S(3)-Pd(1) 8709(14)

C(2)-N(4)-C(5) 1228(3)

C(2)-N(4)-C(9) 1227(3)

C(5)-N(4)-C(9) 1145(3)

N(4)-C(5)-C(6) 1090(3)

N(7)-C(6)-C(5) 1095(3)

C(11)-N(7)-C(8) 1244(3)

C(11)-N(7)-C(6) 1220(3)

C(8)-N(7)-C(6) 1133(3)

N(7)-C(8)-C(9) 1103(3)

N(4)-C(9)-C(8) 1100(3)

C(11)-S(10)-Pd(2) 8619(13)

N(7)-C(11)-S(12) 1234(3)

N(7)-C(11)-S(10) 1253(3)

S(12)-C(11)-S(10) 1112(2)

C(11)-S(12)-Pd(2) 8729(13)

C(18)-C(13)-C(14) 1183(4)

C(18)-C(13)-P(1) 1234(3)

C(14)-C(13)-P(1) 1183(3)

C(13)-C(14)-C(15) 1211(5)

C(16)-C(15)-C(14) 1195(5)

C(17)-C(16)-C(15) 1194(5)

C(16)-C(17)-C(18) 1223(5)

C(13)-C(18)-C(17) 1192(5)

C(24)-C(19)-C(20) 1199(4)

C(24)-C(19)-P(1) 1194(3)

C(20)-C(19)-P(1) 1207(4)

C(21)-C(20)-C(19) 1199(5)

C(22)-C(21)-C(20) 1206(6)

C(21)-C(22)-C(23) 1211(5)

C(22)-C(23)-C(24) 1187(6)

214

C(21)-C(22) 1342(9)

C(22)-C(23) 1390(9)

C(23)-C(24) 1402(7)

C(25)-C(30) 1390(5)

C(25)-C(26) 1405(5)

C(26)-C(27) 1377(6)

C(27)-C(28) 1380(6)

C(28)-C(29) 1375(6)

C(29)-C(30) 1380(6)

C(31)-C(32) 1390(6)

C(31)-C(36) 1392(6)

C(32)-C(33) 1387(6)

C(33)-C(34) 1380(8)

C(34)-C(35) 1365(8)

C(35)-C(36) 1384(7)

C(37)-C(42) 1379(6)

C(37)-C(38) 1388(6)

C(38)-C(39) 1382(6)

C(39)-C(40) 1367(7)

C(40)-C(41) 1356(7)

C(41)-C(42) 1386(6)

C(43)-C(44) 1381(6)

C(43)-C(48) 1393(6)

C(44)-C(45) 1394(7)

C(45)-C(46) 1373(8)

C(46)-C(47) 1365(8)

C(47)-C(48) 1390(6)

C(49)-C(50) 1388(5)

C(49)-C(54) 1402(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1360(6)

C(52)-C(53) 1384(6)

C(53)-C(54) 1372(6)

C(55)-C(56) 1390(5)

C(55)-C(60) 1393(5)

C(56)-C(57) 1385(6)

C(57)-C(58) 1374(6)

C(58)-C(59) 1375(6)

C(59)-C(60) 1377(6)

C(61)-C(66) 1393(6)

C(61)-C(62) 1394(6)

C(62)-C(63) 1388(6)

C(63)-C(64) 1379(7)

C(64)-C(65) 1373(7)

C(65)-C(66) 1384(6)

C(67)-C(72) 1387(6)

C(67)-C(68) 1387(6)

C(68)-C(69) 1378(6)

C(69)-C(70) 1362(7)

C(70)-C(71) 1375(8)

C(71)-C(72) 1376(7)

C(73)-C(78) 1371(6)

C(73)-C(74) 1392(6)

C(74)-C(75) 1371(7)

C(75)-C(76) 1369(8)

C(76)-C(77) 1376(8)

C(77)-C(78) 1410(6)

C(79)-C(84) 1384(5)

C(79)-C(80) 1394(5)

C(80)-C(81) 1374(6)

C(81)-C(82) 1387(6)

C(19)-C(24)-C(23) 1198(5)

C(30)-C(25)-C(26) 1184(4)

C(30)-C(25)-P(1) 1208(3)

C(26)-C(25)-P(1) 1207(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1200(4)

C(29)-C(28)-C(27) 1201(4)

C(28)-C(29)-C(30) 1205(4)

C(29)-C(30)-C(25) 1204(4)

C(32)-C(31)-C(36) 1193(4)

C(32)-C(31)-P(2) 1192(3)

C(36)-C(31)-P(2) 1214(4)

C(33)-C(32)-C(31) 1204(5)

C(34)-C(33)-C(32) 1195(5)

C(35)-C(34)-C(33) 1205(5)

C(34)-C(35)-C(36) 1207(5)

C(35)-C(36)-C(31) 1196(5)

C(42)-C(37)-C(38) 1188(4)

C(42)-C(37)-P(2) 1230(3)

C(38)-C(37)-P(2) 1180(3)

C(39)-C(38)-C(37) 1200(4)

C(40)-C(39)-C(38) 1204(5)

C(41)-C(40)-C(39) 1201(4)

C(40)-C(41)-C(42) 1204(5)

C(37)-C(42)-C(41) 1203(4)

C(44)-C(43)-C(48) 1202(4)

C(44)-C(43)-P(2) 1243(4)

C(48)-C(43)-P(2) 1154(3)

C(43)-C(44)-C(45) 1192(5)

C(46)-C(45)-C(44) 1201(5)

C(47)-C(46)-C(45) 1211(5)

C(46)-C(47)-C(48) 1196(5)

C(47)-C(48)-C(43) 1198(5)

C(50)-C(49)-C(54) 1191(4)

C(50)-C(49)-P(3) 1196(3)

C(54)-C(49)-P(3) 1212(3)

C(49)-C(50)-C(51) 1197(4)

C(52)-C(51)-C(50) 1202(4)

C(51)-C(52)-C(53) 1209(4)

C(54)-C(53)-C(52) 1197(4)

C(53)-C(54)-C(49) 1204(4)

C(56)-C(55)-C(60) 1185(4)

C(56)-C(55)-P(3) 1219(3)

C(60)-C(55)-P(3) 1193(3)

C(57)-C(56)-C(55) 1200(4)

C(58)-C(57)-C(56) 1208(4)

C(57)-C(58)-C(59) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(59)-C(60)-C(55) 1209(4)

C(66)-C(61)-C(62) 1187(4)

C(66)-C(61)-P(3) 1201(3)

C(62)-C(61)-P(3) 1211(3)

C(63)-C(62)-C(61) 1199(4)

C(64)-C(63)-C(62) 1208(5)

C(65)-C(64)-C(63) 1194(4)

C(64)-C(65)-C(66) 1207(5)

C(65)-C(66)-C(61) 1204(4)

C(72)-C(67)-C(68) 1191(4)

C(72)-C(67)-P(4) 1188(3)

C(68)-C(67)-P(4) 1215(3)

C(69)-C(68)-C(67) 1199(5)

215

C(82)-C(83) 1375(6)

C(83)-C(84) 1368(5)

P(10)-F(13) 1549(4)

P(10)-F(15) 1560(4)

P(10)-F(14) 1560(3)

P(10)-F(12) 1564(4)

P(10)-F(11) 1582(3)

P(10)-F(16) 1592(3)

P(20)-F(23) 1557(3)

P(20)-F(21) 1565(3)

P(20)-F(26) 1573(3)

P(20)-F(24) 1582(3)

P(20)-F(22) 1584(3)

P(20)-F(25) 1589(3)

O(90)-C(91) 1361(6)

O(90)-C(93) 1397(7)

C(91)-C(92) 1483(8)

C(93)-C(94) 1393(8)

O(90)-C(91) 1341(10)

O(90)-C(93) 1345(10)

C(91)-C(92) 1452(10)

C(93)-C(94) 1451(10)

P(2)-Pd(1)-P(1) 10098(4)

P(2)-Pd(1)-S(3) 16943(4)

P(1)-Pd(1)-S(3) 8822(4)

P(2)-Pd(1)-S(1) 9507(4)

P(1)-Pd(1)-S(1) 16140(4)

S(3)-Pd(1)-S(1) 7504(4)

P(4)-Pd(2)-S(12) 17025(4)

P(4)-Pd(2)-P(3) 10004(4)

S(12)-Pd(2)-P(3) 8970(3)

P(4)-Pd(2)-S(10) 9535(3)

S(12)-Pd(2)-S(10) 7490(3)

P(3)-Pd(2)-S(10) 16452(4)

C(13)-P(1)-C(25) 10983(18)

C(13)-P(1)-C(19) 1033(2)

C(25)-P(1)-C(19) 10175(19)

C(13)-P(1)-Pd(1) 10736(14)

C(25)-P(1)-Pd(1) 10878(12)

C(19)-P(1)-Pd(1) 12519(13)

C(31)-P(2)-C(43) 10980(19)

C(31)-P(2)-C(37) 10173(17)

C(43)-P(2)-C(37) 10461(19)

C(31)-P(2)-Pd(1) 11826(15)

C(43)-P(2)-Pd(1) 10682(14)

C(37)-P(2)-Pd(1) 11481(13)

C(49)-P(3)-C(61) 10500(18)

C(49)-P(3)-C(55) 10370(18)

C(61)-P(3)-C(55) 10515(18)

C(49)-P(3)-Pd(2) 11419(12)

C(61)-P(3)-Pd(2) 11999(13)

C(55)-P(3)-Pd(2) 10732(12)

C(79)-P(4)-C(67) 11063(18)

C(70)-C(69)-C(68) 1209(5)

C(69)-C(70)-C(71) 1194(5)

C(70)-C(71)-C(72) 1209(5)

C(71)-C(72)-C(67) 1197(5)

C(78)-C(73)-C(74) 1201(4)

C(78)-C(73)-P(4) 1194(3)

C(74)-C(73)-P(4) 1189(3)

C(75)-C(74)-C(73) 1205(5)

C(76)-C(75)-C(74) 1197(5)

C(75)-C(76)-C(77) 1209(5)

C(76)-C(77)-C(78) 1196(5)

C(73)-C(78)-C(77) 1191(5)

C(84)-C(79)-C(80) 1198(4)

C(84)-C(79)-P(4) 1151(3)

C(80)-C(79)-P(4) 1246(3)

C(81)-C(80)-C(79) 1192(4)

C(80)-C(81)-C(82) 1206(4)

C(83)-C(82)-C(81) 1199(4)

C(84)-C(83)-C(82) 1201(4)

C(83)-C(84)-C(79) 1205(4)

F(13)-P(10)-F(15) 1779(3)

F(13)-P(10)-F(14) 913(3)

F(15)-P(10)-F(14) 902(3)

F(13)-P(10)-F(12) 903(3)

F(15)-P(10)-F(12) 882(3)

F(14)-P(10)-F(12) 1775(3)

F(13)-P(10)-F(11) 914(2)

F(15)-P(10)-F(11) 901(2)

F(14)-P(10)-F(11) 915(2)

F(12)-P(10)-F(11) 903(2)

F(13)-P(10)-F(16) 891(2)

F(15)-P(10)-F(16) 8948(19)

F(14)-P(10)-F(16) 8896(18)

F(12)-P(10)-F(16) 892(2)

F(11)-P(10)-F(16) 1793(2)

F(23)-P(20)-F(21) 896(2)

F(23)-P(20)-F(26) 923(2)

F(21)-P(20)-F(26) 1778(2)

F(23)-P(20)-F(24) 9177(19)

F(21)-P(20)-F(24) 8826(17)

F(26)-P(20)-F(24) 9056(16)

F(23)-P(20)-F(22) 893(2)

F(21)-P(20)-F(22) 9091(19)

F(26)-P(20)-F(22) 9024(18)

F(24)-P(20)-F(22) 1787(2)

F(23)-P(20)-F(25) 1794(2)

F(21)-P(20)-F(25) 908(2)

F(26)-P(20)-F(25) 873(2)

F(24)-P(20)-F(25) 8868(19)

F(22)-P(20)-F(25) 903(2)

C(91)-O(90)-C(93) 1125(6)

O(90)-C(91)-C(92) 1100(6)

C(94)-C(93)-O(90) 1137(7)

C(91)-O(90)-C(93) 119(2)

O(90)-C(91)-C(92) 1157(17)

O(90)-C(93)-C(94) 1167(17)

216










b = 107032(4) Aring = 78500(4)deg

c = 212565(12) Aring = 88333(3)deg




F(000) 946









217









Pd(1)-P(2) 22888(9)

Pd(1)-P(1) 23146(9)

Pd(1)-S(1) 23388(8)

Pd(1)-S(3) 23479(9)

P(1)-C(7) 1816(4)

P(1)-C(13) 1817(3)

P(1)-C(19) 1825(4)

P(2)-C(25) 1809(4)

P(2)-C(37) 1821(4)

P(2)-C(31) 1822(4)

S(1)-C(2) 1727(4)

C(2)-N(4) 1326(4)

C(2)-S(3) 1714(4)

N(4)-C(5) 1463(5)

N(4)-C(6) 1480(5)

C(5)-C(6)1 1519(6)

C(6)-C(5)1 1519(6)

C(7)-C(8) 1398(6)

C(7)-C(12) 1399(5)

C(8)-C(9) 1378(6)

C(9)-C(10) 1379(7)

C(10)-C(11) 1390(8)

C(11)-C(12) 1369(7)

C(13)-C(14) 1386(6)

C(13)-C(18) 1392(5)

C(14)-C(15) 1389(5)

C(15)-C(16) 1380(6)

C(16)-C(17) 1381(7)

C(17)-C(18) 1397(5)

C(19)-C(24) 1383(6)

C(19)-C(20) 1386(6)

C(20)-C(21) 1388(6)

C(21)-C(22) 1375(8)

C(22)-C(23) 1370(9)

C(23)-C(24) 1407(7)

C(25)-C(30) 1394(6)

C(25)-C(26) 1396(6)

C(26)-C(27) 1379(6)

C(27)-C(28) 1384(8)

C(28)-C(29) 1365(8)

C(29)-C(30) 1395(6)

C(31)-C(32) 1389(5)

C(31)-C(36) 1391(5)

C(32)-C(33) 1392(6)

C(33)-C(34) 1377(7)

C(34)-C(35) 1377(6)

C(8)-C(7)-P(1) 1204(3)

C(12)-C(7)-P(1) 1209(3)

C(9)-C(8)-C(7) 1203(4)

C(8)-C(9)-C(10) 1202(5)

C(9)-C(10)-C(11) 1199(5)

C(12)-C(11)-C(10) 1202(4)

C(11)-C(12)-C(7) 1205(4)

C(14)-C(13)-C(18) 1191(3)

C(14)-C(13)-P(1) 1215(3)

C(18)-C(13)-P(1) 1194(3)

C(13)-C(14)-C(15) 1204(4)

C(16)-C(15)-C(14) 1202(4)

C(15)-C(16)-C(17) 1202(4)

C(16)-C(17)-C(18) 1196(4)

C(13)-C(18)-C(17) 1204(4)

C(24)-C(19)-C(20) 1194(4)

C(24)-C(19)-P(1) 1224(3)

C(20)-C(19)-P(1) 1182(3)

C(19)-C(20)-C(21) 1209(5)

C(22)-C(21)-C(20) 1197(5)

C(23)-C(22)-C(21) 1201(5)

C(22)-C(23)-C(24) 1207(5)

C(19)-C(24)-C(23) 1192(5)

C(30)-C(25)-C(26) 1191(4)

C(30)-C(25)-P(2) 1230(3)

C(26)-C(25)-P(2) 1176(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1197(5)

C(29)-C(28)-C(27) 1206(4)

C(28)-C(29)-C(30) 1204(5)

C(25)-C(30)-C(29) 1196(4)

C(32)-C(31)-C(36) 1189(4)

C(32)-C(31)-P(2) 1257(3)

C(36)-C(31)-P(2) 1153(3)

C(31)-C(32)-C(33) 1198(4)

C(34)-C(33)-C(32) 1207(4)

C(35)-C(34)-C(33) 1198(4)

C(34)-C(35)-C(36) 1200(4)

C(35)-C(36)-C(31) 1207(4)

C(42)-C(37)-C(38) 1184(4)

C(42)-C(37)-P(2) 1189(3)

C(38)-C(37)-P(2) 1227(3)

C(39)-C(38)-C(37) 1197(5)

C(40)-C(39)-C(38) 1206(5)

C(39)-C(40)-C(41) 1208(5)

C(40)-C(41)-C(42) 1197(5)

218

C(35)-C(36) 1387(6)

C(37)-C(42) 1385(6)

C(37)-C(38) 1399(6)

C(38)-C(39) 1392(6)

C(39)-C(40) 1360(8)

C(40)-C(41) 1361(8)

C(41)-C(42) 1394(7)

P(10)-F(14) 1578(10)

P(10)-F(13) 1579(10)

P(10)-F(16) 1597(10)

P(10)-F(12) 1598(10)

P(10)-F(15) 1599(10)

P(10)-F(11) 1614(10)

P(10)-F(11) 1588(13)

P(10)-F(13) 1591(13)

P(10)-F(14) 1592(13)

P(10)-F(12) 1593(13)

P(10)-F(16) 1595(13)

P(10)-F(15) 1598(13)

P(20)-F(25) 1551(11)

P(20)-F(24) 1557(12)

P(20)-F(26) 1563(11)

P(20)-F(22) 1566(11)

P(20)-F(21) 1575(11)

P(20)-F(23) 1585(11)

P(20)-F(23) 1521(11)

P(20)-F(21) 1545(11)

P(20)-F(26) 1559(11)

P(20)-F(24) 1560(11)

P(20)-F(22) 1585(11)

P(20)-F(25) 1628(11)

P(2)-Pd(1)-P(1) 9715(3)

P(2)-Pd(1)-S(1) 9505(3)

P(1)-Pd(1)-S(1) 16705(3)

P(2)-Pd(1)-S(3) 16837(3)

P(1)-Pd(1)-S(3) 9298(3)

S(1)-Pd(1)-S(3) 7536(3)

C(7)-P(1)-C(13) 10326(17)

C(7)-P(1)-C(19) 10743(19)

C(13)-P(1)-C(19) 10434(17)

C(7)-P(1)-Pd(1) 11069(13)

C(13)-P(1)-Pd(1) 12157(12)

C(19)-P(1)-Pd(1) 10864(13)

C(25)-P(2)-C(37) 10169(18)

C(25)-P(2)-C(31) 11326(17)

C(37)-P(2)-C(31) 10528(17)

C(25)-P(2)-Pd(1) 11377(13)

C(37)-P(2)-Pd(1) 11311(12)

C(31)-P(2)-Pd(1) 10929(13)

C(2)-S(1)-Pd(1) 8589(12)

N(4)-C(2)-S(3) 1233(3)

N(4)-C(2)-S(1) 1239(3)

S(3)-C(2)-S(1) 11276(19)

C(2)-S(3)-Pd(1) 8590(13)

C(2)-N(4)-C(5) 1234(3)

C(2)-N(4)-C(6) 1228(3)

C(5)-N(4)-C(6) 1133(3)

N(4)-C(5)-C(6)1 1090(3)

N(4)-C(6)-C(5)1 1087(3)

C(8)-C(7)-C(12) 1188(4)

C(37)-C(42)-C(41) 1208(4)

F(14)-P(10)-F(13) 910(7)

F(14)-P(10)-F(16) 912(6)

F(13)-P(10)-F(16) 912(6)

F(14)-P(10)-F(12) 1781(8)

F(13)-P(10)-F(12) 901(7)

F(16)-P(10)-F(12) 904(7)

F(14)-P(10)-F(15) 902(7)

F(13)-P(10)-F(15) 1783(8)

F(16)-P(10)-F(15) 901(7)

F(12)-P(10)-F(15) 886(7)

F(14)-P(10)-F(11) 901(7)

F(13)-P(10)-F(11) 894(7)

F(16)-P(10)-F(11) 1785(9)

F(12)-P(10)-F(11) 883(6)

F(15)-P(10)-F(11) 893(6)

F(11)-P(10)-F(13) 904(8)

F(11)-P(10)-F(14) 902(8)

F(13)-P(10)-F(14) 903(8)

F(11)-P(10)-F(12) 902(8)

F(13)-P(10)-F(12) 901(8)

F(14)-P(10)-F(12) 1795(11)

F(11)-P(10)-F(16) 1794(11)

F(13)-P(10)-F(16) 902(8)

F(14)-P(10)-F(16) 899(8)

F(12)-P(10)-F(16) 897(8)

F(11)-P(10)-F(15) 898(8)

F(13)-P(10)-F(15) 1798(12)

F(14)-P(10)-F(15) 899(8)

F(12)-P(10)-F(15) 897(8)

F(16)-P(10)-F(15) 896(8)

F(25)-P(20)-F(24) 911(7)

F(25)-P(20)-F(26) 923(7)

F(24)-P(20)-F(26) 911(7)

F(25)-P(20)-F(22) 916(7)

F(24)-P(20)-F(22) 1766(10)

F(26)-P(20)-F(22) 908(7)

F(25)-P(20)-F(21) 899(7)

F(24)-P(20)-F(21) 902(8)

F(26)-P(20)-F(21) 1774(9)

F(22)-P(20)-F(21) 878(7)

F(25)-P(20)-F(23) 1786(10)

F(24)-P(20)-F(23) 894(7)

F(26)-P(20)-F(23) 890(7)

F(22)-P(20)-F(23) 879(7)

F(21)-P(20)-F(23) 888(7)

F(23)-P(20)-F(21) 941(7)

F(23)-P(20)-F(26) 932(7)

F(21)-P(20)-F(26) 1724(8)

F(23)-P(20)-F(24) 939(7)

F(21)-P(20)-F(24) 907(7)

F(26)-P(20)-F(24) 910(7)

F(23)-P(20)-F(22) 931(7)

F(21)-P(20)-F(22) 887(7)

F(26)-P(20)-F(22) 886(7)

F(24)-P(20)-F(22) 1730(8)

F(23)-P(20)-F(25) 1771(9)

F(21)-P(20)-F(25) 878(7)

F(26)-P(20)-F(25) 849(7)

F(24)-P(20)-F(25) 883(7)

F(22)-P(20)-F(25) 847(6)

219










b = 1085381(18) Aring = 1065109(16)deg

c = 267343(4) Aring = 90deg




F(000) 4112








220











Pd(1)-P(2) 22811(15)

Pd(1)-S(1) 23190(15)

Pd(1)-P(1) 23297(15)

Pd(1)-S(3) 23720(16)

Pd(2)-P(4) 22915(17)

Pd(2)-S(9) 23180(15)

Pd(2)-P(3) 23298(16)

Pd(2)-S(10) 23735(17)

P(1)-C(37) 1820(7)

P(1)-C(25) 1826(7)

P(1)-C(31) 1832(7)

P(2)-C(43) 1814(6)

P(2)-C(49) 1820(6)

P(2)-C(55) 1826(7)

P(3)-C(61) 1832(9)

P(3)-C(67) 1832(7)

P(3)-C(73) 1837(7)

P(4)-C(85) 1815(7)

P(4)-C(79) 1829(7)

P(4)-C(91) 1833(6)

S(1)-C(2) 1715(7)

C(2)-N(4) 1323(8)

C(2)-S(3) 1718(6)

N(4)-C(5) 1470(8)

N(4)-C(11) 1475(8)

C(5)-C(6) 1518(8)

C(6)-N(7) 1487(8)

N(7)-C(8) 1316(9)

N(7)-C(18) 1463(9)

C(8)-S(9) 1722(7)

C(8)-S(10) 1727(7)

C(11)-C(12) 1500(9)

C(12)-C(13) 1376(11)

C(12)-C(17) 1378(10)

C(13)-C(14) 1385(12)

C(14)-C(15) 1393(14)

C(15)-C(16) 1363(14)

C(16)-C(17) 1377(13)

C(18)-C(19) 1510(11)

C(19)-C(24) 1374(12)

C(19)-C(20) 1406(11)

C(20)-C(21) 1390(15)

C(21)-C(22) 1352(18)

C(22)-C(23) 1395(16)

C(79)-P(4)-Pd(2) 1116(2)

C(91)-P(4)-Pd(2) 1124(20

C(2)-S(1)-Pd(1) 859(2)

N(4)-C(2)-S(1) 1227(5)

N(4)-C(2)-S(3) 1240(5)

S(1)-C(2)-S(3) 1132(4)

C(2)-S(3)-Pd(1) 842(2)

C(2)-N(4)-C(5) 1214(5)

C(2)-N(4)-C(11) 1207(5)

C(5)-N(4)-C(11) 1176(5)

N(4)-C(5)-C(6) 1104(5)

N(7)-C(6)-C(5) 1085(5)

C(8)-N(7)-C(18) 1229(6)

C(8)-N(7)-C(6) 1194(6)

C(18)-N(7)-C(6) 1177(5)

N(7)-C(8)-S(9) 1234(5)

N(7)-C(8)-S(10) 1247(5)

S(9)-C(8)-S(10) 1119(4)

C(8)-S(9)-Pd(2) 873(2)

C(8)-S(10)-Pd(2) 854(2)

N(4)-C(11)-C(12) 1154(5)

C(13)-C(12)-C(17) 1187(7)

C(13)-C(12)-C(11) 1218(6)

C(17)-C(12)-C(11) 1193(6)

C(12)-C(13)-C(14) 1206(8)

C(13)-C(14)-C(15) 1203(9)

C(16)-C(15)-C(14) 1185(8)

C(15)-C(16)-C(17) 1214(8)

C(16)-C(17)-C(12) 1206(8)

N(7)-C(18)-C(19) 1127(6)

C(24)-C(19)-C(20) 1180(8)

C(24)-C(19)-C(18) 1234(7)

C(20)-C(19)-C(18) 1185(8)

C(21)-C(20)-C(19) 1189(10)

C(22)-C(21)-C(20) 1229(9)

C(21)-C(22)-C(23) 1187(10)

C(24)-C(23)-C(22) 1193(10)

C(19)-C(24)-C(23) 1222(8)

C(30)-C(25)-C(26) 1194(6)

C(30)-C(25)-P(1) 1211(5)

C(26)-C(25)-P(1) 1194(5)

C(27)-C(26)-C(25) 1195(7)

C(28)-C(27)-C(26) 1206(7)

221

C(23)-C(24) 1389(12)

C(25)-C(30) 1387(10)

C(25)-C(26) 1396(9)

C(26)-C(27) 1392(10)

C(27)-C(28) 1372(12)

C(28)-C(29) 1373(12)

C(29)-C(30) 1391(10)

C(31)-C(32) 1392(9)

C(31)-C(36) 1404(9)

C(32)-C(33) 1390(10)

C(33)-C(34) 1390(13)

C(34)-C(35) 1368(13)

C(35)-C(36) 1396(11)

C(37)-C(42) 1387(10)

C(37)-C(38) 1393(10)

C(38)-C(39) 1387(10)

C(39)-C(40) 1361(12)

C(40)-C(41) 1385(12)

C(41)-C(42) 1390(10)

C(43)-C(48) 1396(10)

C(43)-C(44) 1400(10)

C(44)-C(45) 1370(10)

C(45)-C(46) 1379(12)

C(46)-C(47) 1382(13)

C(47)-C(48) 1400(11)

C(49)-C(54) 1384(11)

C(49)-C(50) 1400(10)

C(50)-C(51) 1380(9)

C(51)-C(52) 1377(14)

C(52)-C(53) 1362(15)

C(53)-C(54) 1399(11)

C(55)-C(60) 1380(9)

C(55)-C(56) 1407(9)

C(56)-C(57) 1370(10)

C(57)-C(58) 1381(11)

C(58)-C(59) 1402(12)

C(59)-C(60) 1373(11)

C(61)-C(62) 1375(11)

C(61)-C(66) 1404(11)

C(62)-C(63) 1395(11)

C(63)-C(64) 1402(14)

C(64)-C(65) 1358(16)

C(65)-C(66) 1377(14)

C(67)-C(68) 1379(11)

C(67)-C(72) 1401(11)

C(68)-C(69) 1386(11)

C(69)-C(70) 1394(14)

C(70)-C(71) 1376(15)

C(71)-C(72) 1391(12)

C(73)-C(78) 1391(11)

C(73)-C(74) 1400(9)

C(74)-C(75) 1393(13)

C(75)-C(76) 1391(14)

C(76)-C(77) 1394(12)

C(77)-C(78) 1384(13)

C(79)-C(84) 1376(11)

C(79)-C(80) 1402(10)

C(80)-C(81) 1399(10)

C(81)-C(82) 1371(13)

C(82)-C(83) 1384(12)

C(83)-C(84) 1379(10)

C(27)-C(28)-C(29) 1202(7)

C(28)-C(29)-C(30) 1202(7)

C(25)-C(30)-C(29) 1201(7)

C(32)-C(31)-C(36) 1189(6)

C(32)-C(31)-P(1) 1203(5)

C(36)-C(31)-P(1) 1208(5)

C(33)-C(32)-C(31) 1208(7)

C(32)-C(33)-C(34) 1204(7)

C(35)-C(34)-C(33) 1187(7)

C(34)-C(35)-C(36) 1224(7)

C(35)-C(36)-C(31) 1188(7)

C(42)-C(37)-C(38) 1181(6)

C(42)-C(37)-P(1) 1194(5)

C(38)-C(37)-P(1) 1224(5)

C(39)-C(38)-C(37) 1210(7)

C(40)-C(39)-C(38) 1202(7)

C(39)-C(40)-C(41) 1200(7)

C(40)-C(41)-C(42) 1200(7)

C(37)-C(42)-C(41) 1206(7)

C(48)-C(43)-C(44) 1199(6)

C(48)-C(43)-P(2) 1250(6)

C(44)-C(43)-P(2) 1151(5)

C(45)-C(44)-C(43) 1201(7)

C(44)-C(45)-C(46) 1205(7)

C(45)-C(46)-C(47) 1202(7)

C(46)-C(47)-C(48) 1204(7)

C(43)-C(48)-C(47) 1189(8)

C(54)-C(49)-C(50) 1205(6)

C(54)-C(49)-P(2) 1209(6)

C(50)-C(49)-P(2) 1185(5)

C(51)-C(50)-C(49) 1197(7)

C(52)-C(51)-C(50) 1198(8)

C(53)-C(52)-C(51) 1205(7)

C(52)-C(53)-C(54) 1213(8)

C(49)-C(54)-C(53) 1181(8)

C(60)-C(55)-C(56) 1188(6)

C(60)-C(55)-P(2) 1235(5)

C(56)-C(55)-P(2) 1177(5)

C(57)-C(56)-C(55) 1198(6)

C(56)-C(57)-C(58) 1213(7)

C(57)-C(58)-C(59) 1190(7)

C(60)-C(59)-C(58) 1197(7)

C(59)-C(60)-C(55) 1213(7)

C(62)-C(61)-C(66) 1196(8)

C(62)-C(61)-P(3) 1193(6)

C(66)-C(61)-P(3) 1208(7)

C(61)-C(62)-C(63) 1218(8)

C(62)-C(63)-C(64) 1176(9)

C(65)-C(64)-C(63) 1203(8)

C(64)-C(65)-C(66) 1224(9)

C(65)-C(66)-C(61) 1183(9)

C(68)-C(67)-C(72) 1195(7)

C(68)-C(67)-P(3) 1198(6)

C(72)-C(67)-P(3) 1204(6)

C(67)-C(68)-C(69) 1210(8)

C(68)-C(69)-C(70) 1192(8)

C(71)-C(70)-C(69) 1205(8)

C(70)-C(71)-C(72) 1202(9)

C(71)-C(72)-C(67) 1196(9)

C(78)-C(73)-C(74) 1186(7)

C(78)-C(73)-P(3) 1212(5)

222

C(85)-C(90) 1379(11)

C(85)-C(86) 1391(10)

C(86)-C(87) 1391(10)

C(87)-C(88) 1387(15)

C(88)-C(89) 1371(14)

C(89)-C(90) 1390(11)

C(91)-C(92) 1379(9)

C(91)-C(96) 1387(9)

C(92)-C(93) 1393(11)

C(93)-C(94) 1368(12)

C(94)-C(95) 1397(11)

C(95)-C(96) 1375(10)

P(10)-F(11) 1550(6)

P(10)-F(15) 1576(5)

P(10)-F(13) 1584(6)

P(10)-F(14) 1590(6)

P(10)-F(12) 1600(5)

P(10)-F(16) 1600(7)

P(20)-F(26) 1543(8)

P(20)-F(21) 1565(8)

P(20)-F(25) 1565(5)

P(20)-F(22) 1568(6)

P(20)-F(24) 1571(6)

P(20)-F(23) 1581(5)

P(2)-Pd(1)-S(1) 9072(5)

P(2)-Pd(1)-P(1) 9793(6)

S(1)-Pd(1)-P(1) 16824(5)

P(2)-Pd(1)-S(3) 16550(6)

S(1)-Pd(1)-S(3) 7528(5)

P(1)-Pd(1)-S(3) 9647(5)

P(4)-Pd(2)-S(9) 9136(5)

P(4)-Pd(2)-P(3) 9795(6)

S(9)-Pd(2)-P(3) 17015(6)

P(4)-Pd(2)-S(10) 16641(6)

S(9)-Pd(2)-S(10) 7505(5)

P(3)-Pd(2)-S(10) 9564(6)

C(37)-P(1)-C(25) 1061(3)

C(37)-P(1)-C(31) 1040(3)

C(25)-P(1)-C(31) 1013(3)

C(37)-P(1)-Pd(1) 1142(2)

C(25)-P(1)-Pd(1) 1091(2)

C(31)-P(1)-Pd(1) 1205(2)

C(43)-P(2)-C(49) 1115(3)

C(43)-P(2)-C(55) 1047(3)

C(49)-P(2)-C(55) 1020(3)

C(43)-P(2)-Pd(1) 1110(2)

C(49)-P(2)-Pd(1) 1132(2)

C(55)-P(2)-Pd(1) 1139(2)

C(61)-P(3)-C(67) 1067(4)

C(61)-P(3)-C(73) 1028(4)

C(67)-P(3)-C(73) 1047(4)

C(61)-P(3)-Pd(2) 1087(3)

C(67)-P(3)-Pd(2) 1122(3)

C(73)-P(3)-Pd(2) 1207(2)

C(85)-P(4)-C(79) 1107(3)

C(85)-P(4)-C(91) 1023(3)

C(79)-P(4)-C(91) 1052(3)

C(85)-P(4)-Pd(2) 1139(3)

C(74)-C(73)-P(3) 1202(6)

C(75)-C(74)-C(73) 1202(8)

C(76)-C(75)-C(74) 1199(7)

C(75)-C(76)-C(77) 1207(8)

C(78)-C(77)-C(76) 1186(9)

C(77)-C(78)-C(73) 1220(7)

C(84)-C(79)-C(80) 1205(6)

C(84)-C(79)-P(4) 1249(5)

C(80)-C(79)-P(4) 1146(5)

C(81)-C(80)-C(79) 1181(7)

C(82)-C(81)-C(80) 1211(7)

C(81)-C(82)-C(83) 1197(7)

C(84)-C(83)-C(82) 1203(7)

C(79)-C(84)-C(83) 1201(7)

C(90)-C(85)-C(86) 1198(7)

C(90)-C(85)-P(4) 1219(6)

C(86)-C(85)-P(4) 1183(6)

C(87)-C(86)-C(85) 1201(8)

C(88)-C(87)-C(86) 1198(8)

C(89)-C(88)-C(87) 1195(7)

C(88)-C(89)-C(90) 1212(9)

C(85)-C(90)-C(89) 1195(8)

C(92)-C(91)-C(96) 1197(6)

C(92)-C(91)-P(4) 1225(5)

C(96)-C(91)-P(4) 1177(5)

C(91)-C(92)-C(93) 1198(7)

C(94)-C(93)-C(92) 1209(7)

C(93)-C(94)-C(95) 1189(7)

C(96)-C(95)-C(94) 1207(7)

C(95)-C(96)-C(91) 1201(6)

F(11)-P(10)-F(15) 920(4)

F(11)-P(10)-F(13) 909(4)

F(15)-P(10)-F(13) 1769(4)

F(11)-P(10)-F(14) 909(4)

F(15)-P(10)-F(14) 889(3)

F(13)-P(10)-F(14) 921(4)

F(11)-P(10)-F(12) 902(4)

F(15)-P(10)-F(12) 897(3)

F(13)-P(10)-F(12) 892(3)

F(14)-P(10)-F(12) 1783(3)

F(11)-P(10)-F(16) 1792(4)

F(15)-P(10)-F(16) 885(4)

F(13)-P(10)-F(16) 885(4)

F(14)-P(10)-F(16) 897(4)

F(12)-P(10)-F(16) 892(3)

F(26)-P(20)-F(21) 1790(6)

F(26)-P(20)-F(25) 893(5)

F(21)-P(20)-F(25) 897(5)

F(26)-P(20)-F(22) 932(6)

F(21)-P(20)-F(22) 865(6)

F(25)-P(20)-F(22) 894(4)

F(26)-P(20)-F(24) 875(6)

F(21)-P(20)-F(24) 928(6)

F(25)-P(20)-F(24) 907(3)

F(22)-P(20)-F(24) 1794(6)

F(26)-P(20)-F(23) 889(4)

F(21)-P(20)-F(23) 921(4)

F(25)-P(20)-F(23) 1780(5)

F(22)-P(20)-F(23) 899(3)

F(24)-P(20)-F(23) 901(3)

223





224




05(C H2 Cl2)






b = 192506(5) Aring = 970520(16)deg

c = 494978(9) Aring = 90deg




F(000) 8880
















225


Pd(1A)-P(2A) 23045(9)

Pd(1A)-P(1A) 23091(9)

Pd(1A)-S(1A) 23294(9)

Pd(1A)-S(3A) 23458(9)

P(1A)-C(22A) 1817(3)

P(1A)-C(28A) 1820(3)

P(1A)-C(16A) 1821(3)

P(1A)-C(22) 1838(8)

P(2A)-C(46A) 1815(4)

P(2A)-C(34A) 1823(4)

P(2A)-C(40A) 1837(4)

P(2A)-C(40) 1843(6)

S(1A)-C(2A) 1726(3)

C(2A)-N(4A) 1306(4)

C(2A)-S(3A) 1717(4)

N(4A)-C(5A) 1467(5)

N(4A)-C(15A) 1467(4)

C(5A)-C(6A) 1528(5)

C(6A)-C(7A) 1512(5)

C(7A)-Si(8A) 1718(5)

C(7A)-Si(8) 2004(6)

Si(8A)-O(13A) 1602(5)

Si(8A)-O(9A) 1629(6)

Si(8A)-O(11A) 1634(5)

O(9A)-C(10A) 1436(8)

O(11A)-C(12A) 1401(8)

O(13A)-C(14A) 1388(9)

Si(8)-O(9) 1606(8)

Si(8)-O(11) 1618(8)

Si(8)-O(13) 1633(8)

O(9)-C(10) 1422(12)

O(11)-C(12) 1418(13)

O(13)-C(14) 1462(12)

C(16A)-C(21A) 1387(5)

C(16A)-C(17A) 1391(5)

C(17A)-C(18A) 1379(5)

C(18A)-C(19A) 1378(6)

C(19A)-C(20A) 1359(6)

C(20A)-C(21A) 1395(5)

C(22A)-C(23A) 13900

C(22A)-C(27A) 13900

C(23A)-C(24A) 13900

C(24A)-C(25A) 13900

C(25A)-C(26A) 13900

C(26A)-C(27A) 13900

C(22)-C(23) 13900

C(22)-C(27) 13900

C(23)-C(24) 13900

C(24)-C(25) 13900

C(25)-C(26) 13900

C(26)-C(27) 13900

C(28A)-C(33A) 1385(5)

C(28A)-C(29A) 1395(5)

C(29A)-C(30A) 1377(5)

C(30A)-C(31A) 1367(6)

C(31A)-C(32A) 1380(6)

C(32A)-C(33A) 1387(5)

C(34A)-C(35A) 1377(5)

C(34A)-C(39A) 1394(5)

O(13)-Si(8)-C(7A) 1101(4)

C(10)-O(9)-Si(8) 1212(8)

C(12)-O(11)-Si(8) 1233(9)

C(14)-O(13)-Si(8) 1224(8)

C(21A)-C(16A)-C(17A) 1189(3)

C(21A)-C(16A)-P(1A) 1232(3)

C(17A)-C(16A)-P(1A) 1178(3)

C(18A)-C(17A)-C(16A) 1206(4)

C(19A)-C(18A)-C(17A) 1198(4)

C(20A)-C(19A)-C(18A) 1205(4)

C(19A)-C(20A)-C(21A) 1203(4)

C(16A)-C(21A)-C(20A) 1198(4)

C(23A)-C(22A)-C(27A) 1200

C(23A)-C(22A)-P(1A) 1187(3)

C(27A)-C(22A)-P(1A) 1213(3)

C(24A)-C(23A)-C(22A) 1200

C(25A)-C(24A)-C(23A) 1200

C(24A)-C(25A)-C(26A) 1200

C(27A)-C(26A)-C(25A) 1200

C(26A)-C(27A)-C(22A) 1200

C(23)-C(22)-C(27) 1200

C(23)-C(22)-P(1A) 1215(7)

C(27)-C(22)-P(1A) 1185(7)

C(24)-C(23)-C(22) 1200

C(25)-C(24)-C(23) 1200

C(24)-C(25)-C(26) 1200

C(25)-C(26)-C(27) 1200

C(26)-C(27)-C(22) 1200

C(33A)-C(28A)-C(29A) 1187(3)

C(33A)-C(28A)-P(1A) 1220(3)

C(29A)-C(28A)-P(1A) 1193(3)

C(30A)-C(29A)-C(28A) 1205(4)

C(31A)-C(30A)-C(29A) 1205(4)

C(30A)-C(31A)-C(32A) 1199(4)

C(31A)-C(32A)-C(33A) 1202(4)

C(28A)-C(33A)-C(32A) 1202(4)

C(35A)-C(34A)-C(39A) 1196(3)

C(35A)-C(34A)-P(2A) 1178(3)

C(39A)-C(34A)-P(2A) 1226(3)

C(34A)-C(35A)-C(36A) 1199(4)

C(37A)-C(36A)-C(35A) 1198(5)

C(38A)-C(37A)-C(36A) 1203(4)

C(37A)-C(38A)-C(39A) 1204(4)

C(38A)-C(39A)-C(34A) 1200(4)

C(41A)-C(40A)-C(45A) 1200

C(41A)-C(40A)-P(2A) 1219(4)

C(45A)-C(40A)-P(2A) 1181(4)

C(42A)-C(41A)-C(40A) 1200

C(41A)-C(42A)-C(43A) 1200

C(42A)-C(43A)-C(44A) 1200

C(45A)-C(44A)-C(43A) 1200

C(44A)-C(45A)-C(40A) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2A) 1242(5)

C(45)-C(40)-P(2A) 1152(6)

C(40)-C(41)-C(42) 1200

C(43)-C(42)-C(41) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

226

C(35A)-C(36A) 1394(6)

C(36A)-C(37A) 1377(7)

C(37A)-C(38A) 1369(7)

C(38A)-C(39A) 1374(5)

C(40A)-C(41A) 13900

C(40A)-C(45A) 13900

C(41A)-C(42A) 13900

C(42A)-C(43A) 13900

C(43A)-C(44A) 13900

C(44A)-C(45A) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46A)-C(51A) 1374(5)

C(46A)-C(47A) 1390(5)

C(47A)-C(48A) 1378(5)

C(48A)-C(49A) 1366(6)

C(49A)-C(50A) 1372(6)

C(50A)-C(51A) 1397(5)

Pd(1B)-P(2B) 22980(9)

Pd(1B)-P(1B) 23261(9)

Pd(1B)-S(1B) 23293(9)

Pd(1B)-S(3B) 23476(10)

P(1B)-C(28) 1800(6)

P(1B)-C(22B) 1817(3)

P(1B)-C(16B) 1822(3)

P(1B)-C(28B) 1853(3)

P(2B)-C(46B) 1725(3)

P(2B)-C(40) 1811(7)

P(2B)-C(34B) 1819(4)

P(2B)-C(40B) 1849(4)

P(2B)-C(46) 1911(5)

S(1B)-C(2B) 1719(4)

C(2B)-N(4B) 1312(5)

C(2B)-S(3B) 1722(4)

N(4B)-C(15B) 1434(7)

N(4B)-C(5) 1434(11)

N(4B)-C(5B) 1523(9)

N(4B)-C(15) 1553(9)

C(5B)-C(6B) 1527(11)

C(6B)-C(7B) 1513(9)

C(7B)-Si(8B) 1842(7)

Si(8B)-O(11B) 1612(6)

Si(8B)-O(9B) 1626(8)

Si(8B)-O(13B) 1629(5)

O(9B)-C(10B) 1426(12)

O(11B)-C(12B) 1431(10)

O(13B)-C(14B) 1383(10)

C(5)-C(6) 1496(12)

C(6)-C(7) 1488(10)

C(7)-Si(8) 1861(8)

Si(8)-O(9) 1577(9)

Si(8)-O(13) 1600(8)

Si(8)-O(11) 1640(8)

O(9)-C(10) 1372(13)

O(11)-C(12) 1411(10)

O(13)-C(14) 1388(12)

C(16B)-C(17B) 1369(5)

C(44)-C(45)-C(40) 1200

C(51A)-C(46A)-C(47A) 1192(3)

C(51A)-C(46A)-P(2A) 1215(3)

C(47A)-C(46A)-P(2A) 1194(3)

C(48A)-C(47A)-C(46A) 1205(4)

C(49A)-C(48A)-C(47A) 1200(4)

C(48A)-C(49A)-C(50A) 1203(4)

C(49A)-C(50A)-C(51A) 1200(4)

C(46A)-C(51A)-C(50A) 1200(4)

P(2B)-Pd(1B)-P(1B) 9991(3)

P(2B)-Pd(1B)-S(1B) 9282(3)

P(1B)-Pd(1B)-S(1B) 16611(3)

P(2B)-Pd(1B)-S(3B) 16751(4)

P(1B)-Pd(1B)-S(3B) 9257(3)

S(1B)-Pd(1B)-S(3B) 7472(4)

C(28)-P(1B)-C(22B) 1115(3)

C(28)-P(1B)-C(16B) 1024(4)

C(22B)-P(1B)-C(16B) 10549(16)

C(22B)-P(1B)-C(28B) 1015(2)

C(16B)-P(1B)-C(28B) 1044(2)

C(28)-P(1B)-Pd(1B) 1174(3)

C(22B)-P(1B)-Pd(1B) 10938(12)

C(16B)-P(1B)-Pd(1B) 10984(12)

C(28B)-P(1B)-Pd(1B) 1245(2)

C(46B)-P(2B)-C(34B) 1031(2)

C(40)-P(2B)-C(34B) 1057(4)

C(46B)-P(2B)-C(40B) 1035(3)

C(34B)-P(2B)-C(40B) 1050(2)

C(40)-P(2B)-C(46) 994(5)

C(34B)-P(2B)-C(46) 1146(3)

C(46B)-P(2B)-Pd(1B) 12210(18)

C(40)-P(2B)-Pd(1B) 1163(4)

C(34B)-P(2B)-Pd(1B) 11240(13)

C(40B)-P(2B)-Pd(1B) 1092(3)

C(46)-P(2B)-Pd(1B) 10795(19)

C(2B)-S(1B)-Pd(1B) 8727(14)

N(4B)-C(2B)-S(1B) 1242(3)

N(4B)-C(2B)-S(3B) 1247(3)

S(1B)-C(2B)-S(3B) 1111(2)

C(2B)-S(3B)-Pd(1B) 8661(13)

C(2B)-N(4B)-C(15B) 1252(5)

C(2B)-N(4B)-C(5) 1241(9)

C(2B)-N(4B)-C(5B) 1207(6)

C(15B)-N(4B)-C(5B) 1135(6)

C(2B)-N(4B)-C(15) 1156(5)

C(5)-N(4B)-C(15) 1200(9)

N(4B)-C(5B)-C(6B) 1098(7)

C(7B)-C(6B)-C(5B) 1152(7)

C(6B)-C(7B)-Si(8B) 1124(5)

O(11B)-Si(8B)-O(9B) 1112(4)

O(11B)-Si(8B)-O(13B) 1081(3)

O(9B)-Si(8B)-O(13B) 1049(4)

O(11B)-Si(8B)-C(7B) 1091(3)

O(9B)-Si(8B)-C(7B) 1110(4)

O(13B)-Si(8B)-C(7B) 1124(3)

C(10B)-O(9B)-Si(8B) 1228(7)

C(12B)-O(11B)-Si(8B) 1249(6)

C(14B)-O(13B)-Si(8B) 1273(7)

N(4B)-C(5)-C(6) 1110(10)

C(7)-C(6)-C(5) 1143(10)

C(6)-C(7)-Si(8) 1165(7)

227

C(16B)-C(21B) 1378(5)

C(17B)-C(18B) 1386(5)

C(18B)-C(19B) 1359(6)

C(19B)-C(20B) 1360(6)

C(20B)-C(21B) 1384(5)

C(22B)-C(23B) 1383(5)

C(22B)-C(27B) 1385(5)

C(23B)-C(24B) 1384(6)

C(24B)-C(25B) 1362(7)

C(25B)-C(26B) 1364(7)

C(26B)-C(27B) 1373(5)

C(28B)-C(29B) 13900

C(28B)-C(33B) 13900

C(29B)-C(30B) 13900

C(30B)-C(31B) 13900

C(31B)-C(32B) 13900

C(32B)-C(33B) 13900

C(28)-C(29) 13900

C(28)-C(33) 13900

C(29)-C(30) 13900

C(30)-C(31) 13900

C(31)-C(32) 13900

C(32)-C(33) 13900

C(34B)-C(35B) 1381(6)

C(34B)-C(39B) 1396(6)

C(35B)-C(36B) 1394(6)

C(36B)-C(37B) 1388(7)

C(37B)-C(38B) 1363(8)

C(38B)-C(39B) 1383(7)

C(40B)-C(41B) 13900

C(40B)-C(45B) 13900

C(41B)-C(42B) 13900

C(42B)-C(43B) 13900

C(43B)-C(44B) 13900

C(44B)-C(45B) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46B)-C(47B) 13900

C(46B)-C(51B) 13900

C(47B)-C(48B) 13900

C(48B)-C(49B) 13900

C(49B)-C(50B) 13900

C(50B)-C(51B) 13900

C(46)-C(47) 13900

C(46)-C(51) 13900

C(47)-C(48) 13900

C(48)-C(49) 13900

C(49)-C(50) 13900

C(50)-C(51) 13900

P(60)-F(65) 1563(4)

P(60)-F(62) 1570(4)

P(60)-F(64) 1572(4)

P(60)-F(63) 1581(4)

P(60)-F(66) 1592(4)

P(60)-F(61) 1601(4)

P(60)-F(62) 1557(11)

P(60)-F(64) 1562(11)

O(9)-Si(8)-O(13) 1091(6)

O(9)-Si(8)-O(11) 1115(5)

O(13)-Si(8)-O(11) 1066(4)

O(9)-Si(8)-C(7) 1042(6)

O(13)-Si(8)-C(7) 1119(4)

O(11)-Si(8)-C(7) 1135(4)

C(10)-O(9)-Si(8) 1269(9)

C(12)-O(11)-Si(8) 1245(7)

C(14)-O(13)-Si(8) 1277(8)

C(17B)-C(16B)-C(21B) 1181(3)

C(17B)-C(16B)-P(1B) 1190(3)

C(21B)-C(16B)-P(1B) 1229(3)

C(16B)-C(17B)-C(18B) 1213(4)

C(19B)-C(18B)-C(17B) 1199(4)

C(18B)-C(19B)-C(20B) 1197(4)

C(19B)-C(20B)-C(21B) 1206(4)

C(16B)-C(21B)-C(20B) 1204(4)

C(23B)-C(22B)-C(27B) 1181(3)

C(23B)-C(22B)-P(1B) 1225(3)

C(27B)-C(22B)-P(1B) 1194(3)

C(22B)-C(23B)-C(24B) 1204(4)

C(25B)-C(24B)-C(23B) 1204(4)

C(24B)-C(25B)-C(26B) 1198(4)

C(25B)-C(26B)-C(27B) 1203(4)

C(26B)-C(27B)-C(22B) 1209(4)

C(29B)-C(28B)-C(33B) 1200

C(29B)-C(28B)-P(1B) 1201(3)

C(33B)-C(28B)-P(1B) 1199(3)

C(28B)-C(29B)-C(30B) 1200

C(31B)-C(30B)-C(29B) 1200

C(30B)-C(31B)-C(32B) 1200

C(31B)-C(32B)-C(33B) 1200

C(32B)-C(33B)-C(28B) 1200

C(29)-C(28)-C(33) 1200

C(29)-C(28)-P(1B) 1209(5)

C(33)-C(28)-P(1B) 1190(5)

C(30)-C(29)-C(28) 1200

C(29)-C(30)-C(31) 1200

C(30)-C(31)-C(32) 1200

C(33)-C(32)-C(31) 1200

C(32)-C(33)-C(28) 1200

C(35B)-C(34B)-C(39B) 1196(4)

C(35B)-C(34B)-P(2B) 1173(3)

C(39B)-C(34B)-P(2B) 1230(4)

C(34B)-C(35B)-C(36B) 1205(4)

C(37B)-C(36B)-C(35B) 1192(5)

C(38B)-C(37B)-C(36B) 1202(5)

C(37B)-C(38B)-C(39B) 1213(5)

C(38B)-C(39B)-C(34B) 1191(5)

C(41B)-C(40B)-C(45B) 1200

C(41B)-C(40B)-P(2B) 1245(4)

C(45B)-C(40B)-P(2B) 1153(4)

C(40B)-C(41B)-C(42B) 1200

C(43B)-C(42B)-C(41B) 1200

C(44B)-C(43B)-C(42B) 1200

C(43B)-C(44B)-C(45B) 1200

C(44B)-C(45B)-C(40B) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2B) 1183(7)

C(45)-C(40)-P(2B) 1217(7)

C(42)-C(41)-C(40) 1200

228

P(60)-F(63) 1568(11)

P(60)-F(65) 1571(11)

P(60)-F(61) 1585(11)

P(60)-F(66) 1605(11)

P(70)-F(73) 1564(3)

P(70)-F(71) 1570(3)

P(70)-F(74) 1570(3)

P(70)-F(75) 1577(3)

P(70)-F(72) 1586(3)

P(70)-F(76) 1592(3)

C(80)-Cl(82) 1647(11)

C(80)-Cl(81) 1747(11)

C(90)-Cl(92) 165(5)

C(90)-Cl(91) 185(7)

P(2A)-Pd(1A)-P(1A) 10199(3)

P(2A)-Pd(1A)-S(1A) 9315(3)

P(1A)-Pd(1A)-S(1A) 16444(3)

P(2A)-Pd(1A)-S(3A) 16753(3)

P(1A)-Pd(1A)-S(3A) 8973(3)

S(1A)-Pd(1A)-S(3A) 7492(3)

C(22A)-P(1A)-C(28A) 1062(2)

C(22A)-P(1A)-C(16A) 1044(2)

C(28A)-P(1A)-C(16A) 10468(16)

C(28A)-P(1A)-C(22) 960(5)

C(16A)-P(1A)-C(22) 1101(5)

C(22A)-P(1A)-Pd(1A) 10918(18)

C(28A)-P(1A)-Pd(1A) 12376(11)

C(16A)-P(1A)-Pd(1A) 10703(12)

C(22)-P(1A)-Pd(1A) 1144(4)

C(46A)-P(2A)-C(34A) 10586(16)

C(46A)-P(2A)-C(40A) 989(3)

C(34A)-P(2A)-C(40A) 1086(3)

C(46A)-P(2A)-C(40) 1060(4)

C(34A)-P(2A)-C(40) 1032(4)

C(46A)-P(2A)-Pd(1A) 11826(12)

C(34A)-P(2A)-Pd(1A) 11366(12)

C(40A)-P(2A)-Pd(1A) 1103(3)

C(40)-P(2A)-Pd(1A) 1086(4)

C(2A)-S(1A)-Pd(1A) 8685(13)

N(4A)-C(2A)-S(3A) 1252(3)

N(4A)-C(2A)-S(1A) 1234(3)

S(3A)-C(2A)-S(1A) 1114(2)

C(2A)-S(3A)-Pd(1A) 8652(12)

C(2A)-N(4A)-C(5A) 1217(3)

C(2A)-N(4A)-C(15A) 1220(3)

C(5A)-N(4A)-C(15A) 1162(3)

N(4A)-C(5A)-C(6A) 1100(3)

C(7A)-C(6A)-C(5A) 1121(3)

C(6A)-C(7A)-Si(8A) 1149(3)

C(6A)-C(7A)-Si(8) 1142(3)

O(13A)-Si(8A)-O(9A) 1067(3)

O(13A)-Si(8A)-O(11A) 1115(3)

O(9A)-Si(8A)-O(11A) 1063(3)

O(13A)-Si(8A)-C(7A) 1115(3)

O(9A)-Si(8A)-C(7A) 1113(3)

O(11A)-Si(8A)-C(7A) 1093(3)

C(10A)-O(9A)-Si(8A) 1226(5)

C(12A)-O(11A)-Si(8A) 1220(5)

C(14A)-O(13A)-Si(8A) 1221(6)

O(9)-Si(8)-O(11) 1128(5)

C(41)-C(42)-C(43) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

C(44)-C(45)-C(40) 1200

C(47B)-C(46B)-C(51B) 1200

C(47B)-C(46B)-P(2B) 1224(3)

C(51B)-C(46B)-P(2B) 1176(3)

C(46B)-C(47B)-C(48B) 1200

C(47B)-C(48B)-C(49B) 1200

C(50B)-C(49B)-C(48B) 1200

C(49B)-C(50B)-C(51B) 1200

C(50B)-C(51B)-C(46B) 1200

C(47)-C(46)-C(51) 1200

C(47)-C(46)-P(2B) 1201(3)

C(51)-C(46)-P(2B) 1199(3)

C(48)-C(47)-C(46) 1200

C(49)-C(48)-C(47) 1200

C(50)-C(49)-C(48) 1200

C(49)-C(50)-C(51) 1200

C(50)-C(51)-C(46) 1200

F(65)-P(60)-F(62) 921(3)

F(65)-P(60)-F(64) 890(3)

F(62)-P(60)-F(64) 1789(4)

F(65)-P(60)-F(63) 1788(3)

F(62)-P(60)-F(63) 887(3)

F(64)-P(60)-F(63) 902(3)

F(65)-P(60)-F(66) 899(3)

F(62)-P(60)-F(66) 900(3)

F(64)-P(60)-F(66) 903(3)

F(63)-P(60)-F(66) 910(3)

F(65)-P(60)-F(61) 901(3)

F(62)-P(60)-F(61) 893(3)

F(64)-P(60)-F(61) 903(3)

F(63)-P(60)-F(61) 890(3)

F(66)-P(60)-F(61) 1793(4)

F(62)-P(60)-F(64) 1789(9)

F(62)-P(60)-F(63) 890(7)

F(64)-P(60)-F(63) 910(7)

F(62)-P(60)-F(65) 896(7)

F(64)-P(60)-F(65) 904(7)

F(63)-P(60)-F(65) 1783(9)

F(62)-P(60)-F(61) 904(7)

F(64)-P(60)-F(61) 907(7)

F(63)-P(60)-F(61) 901(7)

F(65)-P(60)-F(61) 909(7)

F(62)-P(60)-F(66) 901(7)

F(64)-P(60)-F(66) 888(7)

F(63)-P(60)-F(66) 893(7)

F(65)-P(60)-F(66) 897(7)

F(61)-P(60)-F(66) 1792(10)

F(73)-P(70)-F(71) 910(2)

F(73)-P(70)-F(74) 912(2)

F(71)-P(70)-F(74) 8971(19)

F(73)-P(70)-F(75) 1774(2)

F(71)-P(70)-F(75) 8995(18)

F(74)-P(70)-F(75) 913(2)

F(73)-P(70)-F(72) 898(2)

F(71)-P(70)-F(72) 9080(18)

F(74)-P(70)-F(72) 1789(2)

F(75)-P(70)-F(72) 8775(19)

F(73)-P(70)-F(76) 8966(18)

229

O(9)-Si(8)-O(13) 1017(5)

O(11)-Si(8)-O(13) 1130(5)

O(9)-Si(8)-C(7A) 1118(5)

O(11)-Si(8)-C(7A) 1074(4)

F(71)-P(70)-F(76) 1790(2)

F(74)-P(70)-F(76) 8954(17)

F(75)-P(70)-F(76) 8944(18)

F(72)-P(70)-F(76) 8994(17)

Cl(82)-C(80)-Cl(81) 1144(7)

Cl(92)-C(90)-Cl(91) 1077(16)











230

b = 147655(6) Aring = 76579(4)deg

c = 162359(7) Aring = 81131(3)deg




F(000) 1228

















Pd(1)-P(2) 22919(8)

Pd(1)-P(1) 23209(8)

Pd(1)-S(1) 23312(8)

Pd(1)-S(3) 23603(8)

P(1)-C(37) 1818(3)

P(1)-C(31) 1820(4)

P(1)-C(25) 1823(4)

P(2)-C(43) 1813(4)

P(2)-C(55) 1820(4)

P(2)-C(49) 1834(3)

S(1)-C(2) 1724(4)

C(2)-N(4) 1310(5)

C(2)-S(3) 1724(3)

N(4)-C(15) 1475(5)

N(4)-C(5) 1483(5)

C(5)-C(6) 1505(6)

C(6)-C(7) 1489(7)

C(7)-Si(8) 1873(5)

Si(8)-O(11) 1496(7)

Si(8)-O(13) 1557(11)

Si(8)-O(9) 1565(12)

Si(8)-O(9) 1624(6)

Si(8)-O(13) 1633(5)

S(3)-C(2)-S(1) 11213(19)

C(2)-S(3)-Pd(1) 8590(12)

C(2)-N(4)-C(15) 1217(3)

C(2)-N(4)-C(5) 1206(3)

C(15)-N(4)-C(5) 1177(3)

N(4)-C(5)-C(6) 1148(4)

C(7)-C(6)-C(5) 1142(4)

C(6)-C(7)-Si(8) 1144(3)

O(13)-Si(8)-O(9) 1104(10)

O(11)-Si(8)-O(9) 1059(5)

O(11)-Si(8)-O(13) 1110(3)

O(9)-Si(8)-O(13) 1031(4)

O(13)-Si(8)-O(11) 1029(7)

O(9)-Si(8)-O(11) 1063(8)

O(11)-Si(8)-C(7) 1136(3)

O(13)-Si(8)-C(7) 1206(7)

O(9)-Si(8)-C(7) 1088(12)

O(9)-Si(8)-C(7) 1139(6)

O(13)-Si(8)-C(7) 1089(3)

O(11)-Si(8)-C(7) 1069(7)

C(10)-O(9)-Si(8) 1278(8)

C(12)-O(11)-Si(8) 1307(7)

C(14)-O(13)-Si(8) 1264(7)

231

Si(8)-O(11) 1664(11)

O(9)-C(10) 1395(9)

O(11)-C(12) 1457(8)

O(13)-C(14) 1401(9)

O(9)-C(10) 1410(13)

O(11)-C(12) 1438(14)

O(13)-C(14) 1399(14)

C(15)-C(16) 1517(5)

C(16)-C(17) 1540(6)

C(17)-Si(18) 1853(5)

Si(18)-O(19) 1609(4)

Si(18)-O(21) 1614(4)

Si(18)-O(23) 1620(13)

Si(18)-O(23) 1636(5)

Si(18)-O(19) 1649(13)

Si(18)-O(21) 1658(14)

O(19)-C(20) 1413(8)

O(21)-C(22) 1370(9)

O(23)-C(24) 1359(9)

O(19)-C(20) 1398(16)

O(21)-C(22) 1396(17)

O(23)-C(24) 1392(16)

C(25)-C(26) 1393(5)

C(25)-C(30) 1399(5)

C(26)-C(27) 1388(6)

C(27)-C(28) 1372(7)

C(28)-C(29) 1376(7)

C(29)-C(30) 1395(6)

C(31)-C(32) 1388(5)

C(31)-C(36) 1397(5)

C(32)-C(33) 1389(5)

C(33)-C(34) 1383(6)

C(34)-C(35) 1391(5)

C(35)-C(36) 1383(5)

C(37)-C(38) 1395(5)

C(37)-C(42) 1397(5)

C(38)-C(39) 1382(5)

C(39)-C(40) 1393(6)

C(40)-C(41) 1380(6)

C(41)-C(42) 1383(5)

C(43)-C(44) 1387(5)

C(43)-C(48) 1399(5)

C(44)-C(45) 1393(5)

C(45)-C(46) 1383(6)

C(46)-C(47) 1383(6)

C(47)-C(48) 1389(5)

C(49)-C(50) 1384(5)

C(49)-C(54) 1404(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1377(7)

C(52)-C(53) 1384(7)

C(53)-C(54) 1394(5)

C(55)-C(60) 1391(5)

C(55)-C(56) 1394(5)

C(56)-C(57) 1384(6)

C(57)-C(58) 1386(7)

C(58)-C(59) 1382(7)

C(59)-C(60) 1392(6)

P(3)-F(6) 1588(3)

P(3)-F(5) 1590(3)

P(3)-F(3) 1591(3)

C(10)-O(9)-Si(8) 1321(16)

C(12)-O(11)-Si(8) 1203(13)

C(14)-O(13)-Si(8) 1323(16)

N(4)-C(15)-C(16) 1126(3)

C(15)-C(16)-C(17) 1103(3)

C(16)-C(17)-Si(18) 1159(3)

O(19)-Si(18)-O(21) 1125(4)

O(19)-Si(18)-O(23) 1106(3)

O(21)-Si(18)-O(23) 1077(3)

O(23)-Si(18)-O(19) 1101(10)

O(23)-Si(18)-O(21) 1067(11)

O(19)-Si(18)-O(21) 1059(10)

O(19)-Si(18)-C(17) 1084(2)

O(21)-Si(18)-C(17) 1107(4)

O(23)-Si(18)-C(17) 1215(11)

O(23)-Si(18)-C(17) 1068(3)

O(19)-Si(18)-C(17) 1003(9)

O(21)-Si(18)-C(17) 1112(16)

C(20)-O(19)-Si(18) 1270(6)

C(22)-O(21)-Si(18) 1283(6)

C(24)-O(23)-Si(18) 1306(7)

C(20)-O(19)-Si(18) 1250(17)

C(22)-O(21)-Si(18) 1231(18)

C(24)-O(23)-Si(18) 1266(19)

C(26)-C(25)-C(30) 1189(4)

C(26)-C(25)-P(1) 1195(3)

C(30)-C(25)-P(1) 1215(3)

C(27)-C(26)-C(25) 1204(4)

C(28)-C(27)-C(26) 1209(4)

C(27)-C(28)-C(29) 1191(4)

C(28)-C(29)-C(30) 1215(4)

C(29)-C(30)-C(25) 1192(4)

C(32)-C(31)-C(36) 1202(3)

C(32)-C(31)-P(1) 1202(3)

C(36)-C(31)-P(1) 1195(3)

C(31)-C(32)-C(33) 1193(3)

C(34)-C(33)-C(32) 1206(3)

C(33)-C(34)-C(35) 1201(3)

C(36)-C(35)-C(34) 1198(3)

C(35)-C(36)-C(31) 1201(3)

C(38)-C(37)-C(42) 1186(3)

C(38)-C(37)-P(1) 1181(3)

C(42)-C(37)-P(1) 1233(3)

C(39)-C(38)-C(37) 1207(3)

C(38)-C(39)-C(40) 1204(4)

C(41)-C(40)-C(39) 1189(4)

C(40)-C(41)-C(42) 1212(4)

C(41)-C(42)-C(37) 1201(4)

C(44)-C(43)-C(48) 1197(3)

C(44)-C(43)-P(2) 1250(3)

C(48)-C(43)-P(2) 1153(3)

C(43)-C(44)-C(45) 1194(4)

C(46)-C(45)-C(44) 1208(4)

C(45)-C(46)-C(47) 1200(4)

C(46)-C(47)-C(48) 1198(4)

C(47)-C(48)-C(43) 1203(4)

C(50)-C(49)-C(54) 1194(3)

C(50)-C(49)-P(2) 1226(3)

C(54)-C(49)-P(2) 1179(3)

C(49)-C(50)-C(51) 1203(4)

C(52)-C(51)-C(50) 1201(4)

232

P(3)-F(4) 1591(3)

P(3)-F(1) 1591(3)

P(3)-F(2) 1606(3)

P(2)-Pd(1)-P(1) 9913(3)

P(2)-Pd(1)-S(1) 9341(3)

P(1)-Pd(1)-S(1) 16715(3)

P(2)-Pd(1)-S(3) 16839(3)

P(1)-Pd(1)-S(3) 9221(3)

S(1)-Pd(1)-S(3) 7514(3)

C(37)-P(1)-C(31) 10350(15)

C(37)-P(1)-C(25) 10696(16)

C(31)-P(1)-C(25) 10397(16)

C(37)-P(1)-Pd(1) 12280(11)

C(31)-P(1)-Pd(1) 11250(11)

C(25)-P(1)-Pd(1) 10556(11)

C(43)-P(2)-C(55) 11078(16)

C(43)-P(2)-C(49) 10469(16)

C(55)-P(2)-C(49) 10265(16)

C(43)-P(2)-Pd(1) 10997(12)

C(55)-P(2)-Pd(1) 11546(12)

C(49)-P(2)-Pd(1) 11259(11)

C(2)-S(1)-Pd(1) 8681(12)

N(4)-C(2)-S(3) 1239(3)

N(4)-C(2)-S(1) 1239(3)

C(51)-C(52)-C(53) 1203(4)

C(52)-C(53)-C(54) 1200(4)

C(53)-C(54)-C(49) 1198(4)

C(60)-C(55)-C(56) 1195(3)

C(60)-C(55)-P(2) 1194(3)

C(56)-C(55)-P(2) 1210(3)

C(57)-C(56)-C(55) 1198(4)

C(56)-C(57)-C(58) 1207(4)

C(59)-C(58)-C(57) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(55)-C(60)-C(59) 1202(4)

F(6)-P(3)-F(5) 8938(18)

F(6)-P(3)-F(3) 9022(16)

F(5)-P(3)-F(3) 1796(2)

F(6)-P(3)-F(4) 9002(16)

F(5)-P(3)-F(4) 9024(18)

F(3)-P(3)-F(4) 8977(16)

F(6)-P(3)-F(1) 17916(19)

F(5)-P(3)-F(1) 913(2)

F(3)-P(3)-F(1) 8906(18)

F(4)-P(3)-F(1) 904(2)

F(6)-P(3)-F(2) 8873(16)

F(5)-P(3)-F(2) 9101(19)

F(3)-P(3)-F(2) 8896(16)

F(4)-P(3)-F(2) 1782(2)

F(1)-P(3)-F(2) 908(2)

233



example)

iv

Publications








v

Acknowledgements













they are missing








vi












vii

Abstract




























viii










ix

Abbreviations






x

Contents

Declaration ii


Publication iv

Acknowledgement v

Abstract vii

Abbreviations ix

Contents x



1





6












xi

16 References 31






45


51







25 Conclusion 66

26 References 67





73


73



79



xii



84


87




90


35 Conclusion 96

36 References 98





102





112



118




121

45 Conclusion 128

46 References 130

xiii





133




136


(37) 138









148


149


152

55 Conclusion 154

56 References 156


61 Conclusions 158

62 Future work 159

xiv





731 KS2CN(CH2py)2 (1) 163

732 [Au(S2CN(CH2py)2)(PPh3)] (2) 163

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3) 164





738 [Ni(S2C-N(CH2py)2)] (8) 166







170


170


7317 (SC6H4CO2H-4)2 (17) 172

7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18) 172



173


174

xv






741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 178

742 [Pd(S2CNEt2)2] (24) 178



(26) 179

745 [Pd(Me2dazdt)2]I6 (27) 180

746 [PdI2(Me2dazdt)] (28) 180

747 [Pd(Cy2DTO)2]I8 (29) 180



751 (TBA)2[Pd2I6] (30) 186

752 Trans-PdI2(PPh3)2 (31) 186

753 [PdI2(dppe)] (32) 187

754 [PdI2(dppf)] (33) 187







xvi




195


195


196


8 Appendices



201



204



(22)

208



212



216


219



223



223


229



1

























2











(Figure 112)8




3




















4
























5













6














7




















8























9












catalysis









10






























carbon (C-C) bond

11















C)42


12





















metals


13









mechanisms















14



















15

















16














(80)56











17


















18


















19



























20


























21




















22














23












of product92







24
















25






















0

500

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2500

1992 1997 2003 2008 2014

Pri

ce (

USD

pe

r O

z)

Year

Pt

Pd

26





















27



























PGMs112






28



concerns114


















143

29


15 Thesis overview










also investigated



30











31

16 References
























32

37 2466ndash2468

























33























70 Chem Abs 1969 71 114951




34
























35























36


37

























(Figure 211)


38
















manner













39
















mz 200











40




at mz 274


41


































42


































43














44

































45




ligand










Figure 231












46













47






















formulation










48

















complexes
















49















50
































51





nitrogen)

























52


















53





























54




















55


































56




















8764(18)deg]37


57































58


















59
















(Figure 245)








60










NP1 (Figure 246)








61




















0

10

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30

40

50

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70

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100

0 100 200 300 400 500 600 700 800

Wei

ght

(

)

Temperature ()

62


















63







0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

64



















65



0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

66

25 Conclusion















67

26 References





















68























69









70































71

























72

















catalystsrdquo19












73































74
















75






















76









77











Pt(PPh3)2

27

2354(1) 2355(1)

1318 (6)

1723(5) 1725(5)

1118(3)

7467 (4)

Pd(dppf)27

23370(1) 2358(1)

1322(6)

1725(5) 1735(5)

1121(3)

7518(5)

Pd(PPh3)2 (25-A)

23304(10) 23536(10)

1302(5)

1722(4) 1735(4)

1112(2)

7504(4)

Pd(PPh3)2 (25-B)

23388 (8) 23479(9)

1326(4)

1714(4) 1727(4)

11276(19)

7536(3)





(Figure 324)

78












Pd(dppf)26

23348(6) 23516(6) 23347(6) 23445(7)

1313(3) 1323(3)

1728(2) 1719(2) 1709(2) 1723(2)

11188(14) 11215(13)

7507(2) 7498(2)

Pd(PPh3)2 (26)

23720(16) 23190(15) 23735(17) 23180(15

1323(8) 1316(9)

1715(7) 1718(6) 1722(7) 1727(7)

1132(4) 1119(4)

7528(5) 7505(5)

79























80
















81















A

Me MeOH 12 22 95

Et EtOH 51 24 80



B Me MeOH 19 18 80

82



reaction























block and vials





83



























byproducts

84








impact


(SOCDTC)







86

75

8784

87

69

8784

0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Perc

enta

ge y

ield

(

)


22hr 2hr

85


time


















30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Pd loading (mol)

86



















0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Yie

ld

)

Catalyst


87































88










(h)

Yield

()

SD

A

Et

23 2 89 (20)

24 2 83 (10)

25 2 64 (21)

26 2 65 (35)

Pri

23 8 90 (14)

24 24 99 (00)

25 4 97 (12)

26 8 91 (25)

CH2CF3

23 4 92 (10)

24 4 99 (00)

25 2 99 (06)

26 2 95 (17)

B

Me

23 2 66 (02)

24 6 40 (02)

25 2 78 (02)

26 2 46 (44)






89





























90



(mol)

Temperature

(degC)

Time

(h)

Yield

()

A

Me

Me

27 1 100

100

2 87

Pd(OAc)2 1 22 95

Me 27 1 50 2 67

Me Pd(OAc)2 1 50 2 33


catalysts (SOCDTO)










0

20

40

60

80

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

1 mol 2 mol

91


















0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Time (hours)

1 mol 2 mol

92



(mol)

Time

(h)

Yield

()

SD

()

1

1 39 05

A

Pri

27

2 48 06

3 52 07

4 52 09

5 53 08

Pri

27

2

1 74 31

2 79 23

3 81 27

4 83 27

5 83 30

A

CF3CH2

27

2

1 49 05

2 72 09

3 85 11

4 92 00

5 96 05






or 2 hours

93


T = 50 degC








89

9899 99

85

92

9596

75

80

85

90

95

100

105

1 2 3 4

Yie

ld (

)

Time (hours)


40

50

60

70

80

90

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

EtOH iPrOH

94













0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10

Yie

ld (

)

Time (hours)


95







(mol)

Time

(h)

Yield

()

SD

()

2

1 53 11

B

OMe

28

2 95 05

3 100 05

4 100 00

5 100 00

B

OMe

29

2

1 54 20

2 89 08

3 99 02

4 100 00

5 100 00











96




method (100)

35 Conclusion



























97









98

36 References




















99











100






























101













and Singulair56

















102






















secondary source







103
















104























105













above11













sections






106

























107









A

1 mol

Me 2 94 ( 02)

Et 2 43 ( 02)

Pri 2 52 ( 47)

CH2CF3 2 93 ( 30)

2 mol

Me 2 99 ( 04)

EtOH 2 81 ( 33)

Pri 2 75 ( 40)

CH2CF3 2 99 ( 15)













108






















original work

109













50

MeOH

11 Pd

1 34

2 39

5 73

22 87

100

MeOH

11 Pd

1 91

2 90

5 92

22 92







A MeOH 11 22 95

110




















111








nm17

















112






catalyst
















113








0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25

Yiel

d (

)

Time (hours)


114

















0

20

40

60

80

100

120

0 5 10 15 20 25 30

Yiel

d (

)

Time (hours)


115













B Me 1 mol 2 80 (02)

2 mol 2 87 (16)







116





















B

MeOH

1 mol

2 96 ( 02)

4 94 ( 17)

6 96 ( 03)

24 95 (12)

B

MeOH

2 mol

2 99 (06)

4 99 (04)

6 99 (04)

24 99 (05)



117







C AcOH 1 mol 2 61 ( 30)

2 mol 2 83 ( 40)













C

AcOH

1 mol

2 44 ( 28)

4 55 ( 06)

6 62 ( 25)

24 71 ( 16)

C

AcOH

2 mol

2 71 ( 78)

4 71 ( 21)

6 72 ( 13)

24 85 ( 38)

118


















119




























120









coupling reaction



















reading

121













coupling reactions












122


Catalyst Pd

loadings

(mol )

Yield ()


[PdI2(PPh3)2] (31)

05



























123

















coupling reactions




80

85

90

95

100

105


Yiel

d (

)

Catalysts

30 min 60 min

124















K2CO3 in ethanol











125




















80

85

90

95

100

30 60 90

Yie

ld (

)

Time (min)

(TBA)₂[Pd₂I₆] (30) [PdCl₂(PPh₃)₂]

126

















0

10

20

30

40

50

60

70

80

90

100

90 120 150

Pro

du

ct y

ield

(

)

Time (min)


127




60 968 plusmn 04


60 973 plusmn 15


60 996 plusmn 01


60 995 plusmn 01









0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


128










45 Conclusion











0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


129




excellent yield










130

46 References























131
























132
































133














oxidant PhI(OAc)2











134






















135
















products










both complexes







136
















137












138



25-A

23304(10)

23536(10)

1302(5)

1722(4)

1735(4)

1112(2)

7504(4)

36-A

23294(9)

23458(9)

1306(4)

1726(3)

1717(4)

1114(2)

7492(3)

36-B

23293(9)

23476(10)

1312(5)

1719(4)

1722(4)

1111(2)

7472(3)








C(10)-O(9)-Si(8) 1226˚ (5) 1228˚ (7) 02˚

C(12)-O(11)-Si(8) 1220˚ (5) 1249˚ (6) 29˚

C(14)-O(13)-Si(8) 1221˚ (6) 1273˚ (7) 52˚







139











140













Reaction

Catalyst Pd

(mol)

Temperature

(degC)

Time

(h)

Yield

()

SD

A

36

1

100

2

85 ( 06)

37 85 ( 07)

23 87 (10)

141











product








0

10

20

30

40

50

60

70

1 2 3 4 5 6

Yiel

d (

)

Time (hours)

36 37

142



















0

20

40

60

80

100

120

0 1 2 3 4 5 6

Yiel

d (

)


36 37

143









(h)

Yield

()

SD

Et

23 2 89 (20)

A

36 24 99 (04)

37 24 42 (34)

CH2CF3

23 4 92 (10)

36 6 98 (02)

37 6 90 (17)

B Me 23 2 66 (02)

37 6 60 (38)















144





magnetic field14















145






















146



nanoparticles















147



















ethanol and dried









148







and dried















149








complexes













physisorbed

150











nanoparticles


151






















60

65

70

75

80

85

90

95

100

0 100 200 300 400 500 600

Weig

ht (

)

Temperature ()


152



palladium catalyst










h)








153



36SiO2Fe3O4 32 13 5 -

36SiO2Fe3O4 32 27 10 6



























154









55 Conclusion






















155






156

56 References























157










158


61 Conclusions



















donor groups










159

















system

62 Future work













160



161

7 Experimental





























162


























163


731 KS2CN(CH2py)2 (1)








mg (84) IR 2923 (νC-H) 2361 1591 1570 1474 1434 (νC-N) 1358 1302 1183





(100) [M-K]ˉ

732 [Au(S2CN(CH2py)2)(PPh3)] (2)












N 56

164

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3)














37 Found C 497 H 37 N 35















C 585 H 44 N 34

165




















677 H 48 N 41











166









45 N 35











1915 (νCO) 1589 1570 1475 1432 1409 1207 1157 1090 1001 750 689 cmndash1





37 Found C 699 H 47 N 37

738 [Ni(S2C-N(CH2py)2)] (8)




167









H 40 N 138 Found C 433 H 36 N 108




















199616) C 641 H 45 N 14 Found C 637 H 42 N 18

168



















H 43 N 16













169







H 42 N 10












715 H 51 N 10











170











(CO) 1890 (CO) 1531 (OCO) 1481 1433 1391 1184 1090 979 827 743 692 cmndash












= 208951) C 615 H 41 N 13 Found C 614 H 39 N 14








171








226170) C 643 H 39 N 12 Found C 641 H 38 N 12



















C 509 H 33 N 13

172

7317 (SC6H4CO2H-4)2 (17)






2669 2552 1676 (VCO) 1591 1423 1323 1292 1181 1116 933 850 cmndash1 1H NMR



7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18)





















H 42 Found C 586 H 42

173































174









= 138224) C 617 H 42 Found C 617 H 41


















175






1535 1481 1434 1419 1176 1095 862 744 692 cm-1 1H NMR (CD2Cl2) 578 (d







H 33 N 16 Found C 526 H 34 N 17



















176














x 2 2 x 2H PCH2P) 661 (m 4H C6H5) 710 726 738 754 772 794 (m x 6 36H


















177





178


741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 925













742 [Pd(S2CNEt2)2] (24)26













179






(79) IR (ATR) 1514 1480 1434 1280 1239 1094 999 (νC-S) 831 (νPF) cm-1 1H






524 H 38 N 16 Found C 525 H 37 N 16




















180


745 [Pd(Me2dazdt)2]I6 (27)







1429 1393 1357 1330 1287 1283 1107 1073 1028 981 825 743610 581 532


NCH2 JHH = 67 Hz)









1527 1460 1423 1395 1359 1330 1286 1264 1223 1114 1073 1027 958 897



literature28

747 [Pd(Cy2DTO)2]I8 (29)





181







199 H 29 N 33 Found C 203 H 28 N 34
















data

182





183

























184












method data (99)





Hz 20 Hz) 726 (dd 1H J = 80 Hz 10 Hz) 419 (s3H)





3H J = 70 Hz)




60 Hz) 150 (t 6H J = 60 Hz)



185






3H)

186


751 (TBA)2[Pd2I6]30 (30)


























187

753 [PdI2(dppe)] (32)





Yield 325 mg (87) IR 3052 1437 1100 998 877 811 701 688 678 cm-1 1H




754 [PdI2(dppf)] (33)






= 242 (s dppf) ppm







188












step












189






















190






by 1H NMR




746 (dd 1H JHH = 786 Hz 42 Hz) 586 (s2H) 216 (s 3H)











isolated yield

191



















192



















C 310 H 60 N 45












193






H 66 N 31 Found C 341 H 67 N 32



















47 N 14






194





























195






(129 g)














603 563 (νFeO) cm-1









196

SiO236 NP



SiO236 NP











36SiO2Fe3O4


588 (νFeO) cm-1


37SiO2Fe3O4



197










catalyst system





NMR



198

References




















199






















200

2013 49 11358ndash60

201

Appendices



N(CH2py)2)(CO)(PPh3)2] (5)









b = 148523(7) Aring = 82606(3)deg

c = 179728(7) Aring = 87478(3)deg




202

F(000) 1164

















Ru(1)-C(28) 1836(3)

Ru(1)-C(19) 2083(3)

Ru(1)-P(2) 23706(8)

Ru(1)-P(1) 23823(8)

Ru(1)-S(3) 24740(8)

Ru(1)-S(1) 25025(8)

P(1)-C(29) 1834(3)

P(1)-C(35) 1834(3)

P(1)-C(41) 1845(4)

P(2)-C(53) 1827(3)

P(2)-C(59) 1837(3)

P(2)-C(47) 1845(3)

S(1)-C(2) 1715(3)

C(2)-N(4) 1333(4)

C(2)-S(3) 1698(3)

N(4)-C(5) 1457(5)

N(4)-C(12) 1461(4)

C(5)-C(6) 1516(5)

C(6)-N(7) 1344(5)

C(6)-C(11) 1372(5)

N(7)-C(8) 1353(6)

C(8)-C(9) 1382(7)

C(9)-C(10) 1366(7)

C(10)-C(11) 1368(6)

C(12)-C(13) 1519(6)

C(13)-N(14) 1335(5)

C(13)-C(18) 1370(6)

N(14)-C(15) 1360(7)

C(15)-C(16) 1339(9)

C(16)-C(17) 1354(8)

C(17)-C(18) 1398(7)

C(29)-P(1)-Ru(1) 11804(10)

C(35)-P(1)-Ru(1) 11715(11)

C(41)-P(1)-Ru(1) 11341(12)

C(53)-P(2)-C(59) 10292(15)

C(53)-P(2)-C(47) 10443(14)

C(59)-P(2)-C(47) 9991(14)

C(53)-P(2)-Ru(1) 11295(10)

C(59)-P(2)-Ru(1) 11877(11)

C(47)-P(2)-Ru(1) 11586(11)

C(2)-S(1)-Ru(1) 8783(12)

N(4)-C(2)-S(3) 1241(3)

N(4)-C(2)-S(1) 1227(3)

S(3)-C(2)-S(1) 11319(18)

C(2)-S(3)-Ru(1) 8915(11)

C(2)-N(4)-C(5) 1221(3)

C(2)-N(4)-C(12) 1210(3)

C(5)-N(4)-C(12) 1168(3)

N(4)-C(5)-C(6) 1153(3)

N(7)-C(6)-C(11) 1231(4)

N(7)-C(6)-C(5) 1139(3)

C(11)-C(6)-C(5) 1230(3)

C(6)-N(7)-C(8) 1168(4)

N(7)-C(8)-C(9) 1230(4)

C(10)-C(9)-C(8) 1182(4)

C(9)-C(10)-C(11) 1201(4)

C(10)-C(11)-C(6) 1187(4)

N(4)-C(12)-C(13) 1144(3)

N(14)-C(13)-C(18) 1227(4)

N(14)-C(13)-C(12) 1133(4)

C(18)-C(13)-C(12) 1240(3)

C(13)-N(14)-C(15) 1159(5)

203

C(19)-C(20) 1333(5)

C(20)-C(21) 1477(5)

C(21)-C(22) 1395(5)

C(21)-C(26) 1403(5)

C(22)-C(23) 1388(5)

C(23)-C(24) 1386(6)

C(24)-C(25) 1384(6)

C(24)-C(27) 1519(6)

C(25)-C(26) 1386(5)

C(28)-O(28) 1138(4)

C(29)-C(34) 1388(5)

C(29)-C(30) 1397(5)

C(30)-C(31) 1383(5)

C(31)-C(32) 1387(6)

C(32)-C(33) 1378(6)

C(33)-C(34) 1396(5)

C(35)-C(36) 1373(6)

C(35)-C(40) 1393(5)

C(36)-C(37) 1382(5)

C(37)-C(38) 1380(6)

C(38)-C(39) 1359(7)

C(39)-C(40) 1404(5)

C(41)-C(42) 1383(6)

C(41)-C(46) 1393(5)

C(42)-C(43) 1389(7)

C(43)-C(44) 1372(9)

C(44)-C(45) 1371(8)

C(45)-C(46) 1392(6)

C(47)-C(52) 1386(4)

C(47)-C(48) 1393(5)

C(48)-C(49) 1384(5)

C(49)-C(50) 1384(5)

C(50)-C(51) 1381(6)

C(51)-C(52) 1396(5)

C(53)-C(58) 1388(5)

C(53)-C(54) 1393(5)

C(54)-C(55) 1407(5)

C(55)-C(56) 1375(6)

C(56)-C(57) 1384(6)

C(57)-C(58) 1393(5)

C(59)-C(64) 1384(5)

C(59)-C(60) 1395(5)

C(60)-C(61) 1394(5)

C(61)-C(62) 1381(7)

C(62)-C(63) 1378(7)

C(63)-C(64) 1399(5)

C(28)-Ru(1)-C(19) 9900(14)

C(28)-Ru(1)-P(2) 9001(10)

C(19)-Ru(1)-P(2) 8442(9)

C(28)-Ru(1)-P(1) 8661(11)

C(19)-Ru(1)-P(1) 8546(9)

P(2)-Ru(1)-P(1) 16869(3)

C(28)-Ru(1)-S(3) 16962(11)

C(19)-Ru(1)-S(3) 9137(9)

P(2)-Ru(1)-S(3) 9142(3)

P(1)-Ru(1)-S(3) 9385(3)

C(28)-Ru(1)-S(1) 9981(11)

C(19)-Ru(1)-S(1) 16110(9)

P(2)-Ru(1)-S(1) 9381(3)

P(1)-Ru(1)-S(1) 9739(3)

C(16)-C(15)-N(14) 1249(5)

C(15)-C(16)-C(17) 1188(5)

C(16)-C(17)-C(18) 1187(5)

C(13)-C(18)-C(17) 1190(4)

C(20)-C(19)-Ru(1) 1263(2)

C(19)-C(20)-C(21) 1261(3)

C(22)-C(21)-C(26) 1174(3)

C(22)-C(21)-C(20) 1231(3)

C(26)-C(21)-C(20) 1195(3)

C(23)-C(22)-C(21) 1211(3)

C(24)-C(23)-C(22) 1212(4)

C(25)-C(24)-C(23) 1181(4)

C(25)-C(24)-C(27) 1218(4)

C(23)-C(24)-C(27) 1202(4)

C(24)-C(25)-C(26) 1213(3)

C(25)-C(26)-C(21) 1210(3)

O(28)-C(28)-Ru(1) 1776(3)

C(34)-C(29)-C(30) 1192(3)

C(34)-C(29)-P(1) 1224(3)

C(30)-C(29)-P(1) 1183(3)

C(31)-C(30)-C(29) 1202(3)

C(30)-C(31)-C(32) 1204(3)

C(33)-C(32)-C(31) 1196(3)

C(32)-C(33)-C(34) 1204(4)

C(29)-C(34)-C(33) 1201(3)

C(36)-C(35)-C(40) 1179(3)

C(36)-C(35)-P(1) 1208(3)

C(40)-C(35)-P(1) 1214(3)

C(35)-C(36)-C(37) 1214(4)

C(38)-C(37)-C(36) 1208(5)

C(39)-C(38)-C(37) 1187(4)

C(38)-C(39)-C(40) 1210(4)

C(35)-C(40)-C(39) 1202(4)

C(42)-C(41)-C(46) 1184(4)

C(42)-C(41)-P(1) 1223(3)

C(46)-C(41)-P(1) 1193(3)

C(41)-C(42)-C(43) 1208(5)

C(44)-C(43)-C(42) 1201(5)

C(45)-C(44)-C(43) 1201(4)

C(44)-C(45)-C(46) 1201(4)

C(45)-C(46)-C(41) 1205(4)

C(52)-C(47)-C(48) 1186(3)

C(52)-C(47)-P(2) 1223(3)

C(48)-C(47)-P(2) 1189(2)

C(49)-C(48)-C(47) 1207(3)

C(50)-C(49)-C(48) 1203(4)

C(51)-C(50)-C(49) 1196(3)

C(50)-C(51)-C(52) 1200(3)

C(47)-C(52)-C(51) 1207(3)

C(58)-C(53)-C(54) 1197(3)

C(58)-C(53)-P(2) 1197(2)

C(54)-C(53)-P(2) 1199(3)

C(53)-C(54)-C(55) 1196(3)

C(56)-C(55)-C(54) 1201(3)

C(55)-C(56)-C(57) 1204(3)

C(56)-C(57)-C(58) 1200(4)

C(53)-C(58)-C(57) 1203(3)

C(64)-C(59)-C(60) 1194(3)

C(64)-C(59)-P(2) 1210(3)

C(60)-C(59)-P(2) 1196(3)

C(61)-C(60)-C(59) 1201(4)

204

S(3)-Ru(1)-S(1) 6983(3)

C(29)-P(1)-C(35) 10221(15)

C(29)-P(1)-C(41) 10252(17)

C(35)-P(1)-C(41) 10111(16)

C(62)-C(61)-C(60) 1199(4)

C(63)-C(62)-C(61) 1205(4)

C(62)-C(63)-C(64) 1198(4)

C(59)-C(64)-C(63) 1204(4)





5(C H2 Cl2)






b = 217537(9) Aring = 92572(4)deg

c = 304002(14) Aring = 90deg

205




F(000) 3136

















Ru(1)-O(3) 2161(4)

Ru(1)-O(1) 2232(4)

Ru(1)-P(43) 22640(16)

Ru(1)-P(13) 22916(17)

Ru(1)-P(11) 23361(16)

Ru(1)-P(41) 23570(16)

Ru(1)-C(2) 2531(6)

O(1)-C(2) 1267(7)

C(2)-O(3) 1260(7)

C(2)-C(4) 1489(8)

C(4)-C(9) 1370(9)

C(4)-C(5) 1380(8)

C(5)-C(6) 1387(8)

C(6)-N(7) 1333(8)

C(6)-C(6)1 1475(12)

N(7)-C(8) 1338(9)

C(8)-C(9) 1390(9)

P(11)-C(20) 1806(6)

P(11)-C(14) 1818(6)

P(11)-C(12) 1829(6)

C(12)-P(13) 1854(6)

P(13)-C(26) 1815(6)

P(13)-C(32) 1820(6)

C(14)-C(15) 1371(9)

C(14)-C(19) 1395(8)

C(15)-C(16) 1395(9)

C(16)-C(17) 1373(10)

C(5)-C(6)-C(6)1 1212(7)

C(6)-N(7)-C(8) 1175(6)

N(7)-C(8)-C(9) 1236(6)

C(4)-C(9)-C(8) 1180(6)

C(20)-P(11)-C(14) 1050(3)

C(20)-P(11)-C(12) 1088(3)

C(14)-P(11)-C(12) 1074(3)

C(20)-P(11)-Ru(1) 1157(2)

C(14)-P(11)-Ru(1) 1235(2)

C(12)-P(11)-Ru(1) 950(2)

P(11)-C(12)-P(13) 948(3)

C(26)-P(13)-C(32) 1043(3)

C(26)-P(13)-C(12) 1024(3)

C(32)-P(13)-C(12) 1072(3)

C(26)-P(13)-Ru(1) 1188(2)

C(32)-P(13)-Ru(1) 1249(2)

C(12)-P(13)-Ru(1) 958(2)

C(15)-C(14)-C(19) 1200(6)

C(15)-C(14)-P(11) 1205(5)

C(19)-C(14)-P(11) 1194(5)

C(14)-C(15)-C(16) 1200(6)

C(17)-C(16)-C(15) 1194(7)

C(18)-C(17)-C(16) 1208(7)

C(17)-C(18)-C(19) 1202(7)

C(18)-C(19)-C(14) 1195(7)

C(25)-C(20)-C(21) 1195(6)

C(25)-C(20)-P(11) 1227(5)

206

C(17)-C(18) 1370(11)

C(18)-C(19) 1377(9)

C(20)-C(25) 1371(9)

C(20)-C(21) 1395(9)

C(21)-C(22) 1370(10)

C(22)-C(23) 1375(12)

C(23)-C(24) 1383(13)

C(24)-C(25) 1397(11)

C(26)-C(31) 1375(9)

C(26)-C(27) 1402(8)

C(27)-C(28) 1383(9)

C(28)-C(29) 1361(10)

C(29)-C(30) 1388(10)

C(30)-C(31) 1384(10)

C(32)-C(37) 1378(9)

C(32)-C(33) 1412(9)

C(33)-C(34) 1376(10)

C(34)-C(35) 1354(11)

C(35)-C(36) 1381(11)

C(36)-C(37) 1385(9)

P(41)-C(50) 1818(6)

P(41)-C(44) 1823(7)

P(41)-C(42) 1851(6)

C(42)-P(43) 1849(6)

P(43)-C(62) 1811(6)

P(43)-C(56) 1829(7)

C(44)-C(49) 1384(9)

C(44)-C(45) 1387(9)

C(45)-C(46) 1383(10)

C(46)-C(47) 1377(12)

C(47)-C(48) 1386(12)

C(48)-C(49) 1366(11)

C(50)-C(55) 1375(9)

C(50)-C(51) 1398(9)

C(51)-C(52) 1386(9)

C(52)-C(53) 1364(11)

C(53)-C(54) 1385(11)

C(54)-C(55) 1382(10)

C(56)-C(57) 1357(9)

C(56)-C(61) 1388(9)

C(57)-C(58) 1392(10)

C(58)-C(59) 1376(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1380(10)

C(62)-C(63) 1386(9)

C(62)-C(67) 1395(8)

C(63)-C(64) 1396(9)

C(64)-C(65) 1362(10)

C(65)-C(66) 1370(10)

C(66)-C(67) 1385(8)

B(70)-C(83) 1628(11)

B(70)-C(77) 1635(11)

B(70)-C(89) 1644(11)

B(70)-C(71) 1659(10)

C(71)-C(76) 1367(10)

C(71)-C(72) 1398(10)

C(72)-C(73) 1367(11)

C(73)-C(74) 1346(13)

C(74)-C(75) 1370(13)

C(75)-C(76) 1403(11)

C(77)-C(82) 1376(10)

C(21)-C(20)-P(11) 1172(5)

C(22)-C(21)-C(20) 1209(7)

C(21)-C(22)-C(23) 1193(8)

C(22)-C(23)-C(24) 1211(8)

C(23)-C(24)-C(25) 1191(8)

C(20)-C(25)-C(24) 1201(7)

C(31)-C(26)-C(27) 1182(6)

C(31)-C(26)-P(13) 1203(5)

C(27)-C(26)-P(13) 1207(5)

C(28)-C(27)-C(26) 1201(6)

C(29)-C(28)-C(27) 1208(6)

C(28)-C(29)-C(30) 1201(7)

C(31)-C(30)-C(29) 1192(7)

C(26)-C(31)-C(30) 1217(7)

C(37)-C(32)-C(33) 1184(6)

C(37)-C(32)-P(13) 1193(5)

C(33)-C(32)-P(13) 1221(5)

C(34)-C(33)-C(32) 1195(7)

C(35)-C(34)-C(33) 1215(7)

C(34)-C(35)-C(36) 1199(7)

C(35)-C(36)-C(37) 1199(8)

C(32)-C(37)-C(36) 1208(7)

C(50)-P(41)-C(44) 1009(3)

C(50)-P(41)-C(42) 1075(3)

C(44)-P(41)-C(42) 1055(3)

C(50)-P(41)-Ru(1) 1224(2)

C(44)-P(41)-Ru(1) 1243(2)

C(42)-P(41)-Ru(1) 9385(19)

P(43)-C(42)-P(41) 952(3)

C(62)-P(43)-C(56) 1029(3)

C(62)-P(43)-C(42) 1067(3)

C(56)-P(43)-C(42) 1063(3)

C(62)-P(43)-Ru(1) 1294(2)

C(56)-P(43)-Ru(1) 1125(2)

C(42)-P(43)-Ru(1) 970(2)

C(49)-C(44)-C(45) 1201(7)

C(49)-C(44)-P(41) 1214(5)

C(45)-C(44)-P(41) 1185(5)

C(46)-C(45)-C(44) 1188(7)

C(47)-C(46)-C(45) 1211(8)

C(46)-C(47)-C(48) 1195(8)

C(49)-C(48)-C(47) 1200(8)

C(48)-C(49)-C(44) 1206(7)

C(55)-C(50)-C(51) 1187(6)

C(55)-C(50)-P(41) 1226(5)

C(51)-C(50)-P(41) 1185(5)

C(52)-C(51)-C(50) 1195(6)

C(53)-C(52)-C(51) 1208(7)

C(52)-C(53)-C(54) 1203(7)

C(55)-C(54)-C(53) 1188(7)

C(50)-C(55)-C(54) 1218(7)

C(57)-C(56)-C(61) 1194(6)

C(57)-C(56)-P(43) 1190(5)

C(61)-C(56)-P(43) 1214(5)

C(56)-C(57)-C(58) 1204(7)

C(59)-C(58)-C(57) 1206(7)

C(60)-C(59)-C(58) 1184(7)

C(59)-C(60)-C(61) 1214(7)

C(60)-C(61)-C(56) 1197(7)

C(63)-C(62)-C(67) 1188(6)

C(63)-C(62)-P(43) 1211(5)

207

C(77)-C(78) 1406(11)

C(78)-C(79) 1390(11)

C(79)-C(80) 1367(12)

C(80)-C(81) 1350(13)

C(81)-C(82) 1412(12)

C(83)-C(88) 1388(11)

C(83)-C(84) 1410(11)

C(84)-C(85) 1398(12)

C(85)-C(86) 1379(14)

C(86)-C(87) 1372(14)

C(87)-C(88) 1399(12)

C(89)-C(94) 1392(10)

C(89)-C(90) 1412(10)

C(90)-C(91) 1387(11)

C(91)-C(92) 1365(13)

C(92)-C(93) 1353(12)

C(93)-C(94) 1402(11)

C(100)-Cl(2) 1707(11)

C(100)-Cl(1) 1727(11)

C(110)-Cl(4) 1639(14)

C(110)-Cl(3) 1720(12)

C(120)-Cl(5) 1670(15)

C(120)-Cl(6) 1751(16)

O(3)-Ru(1)-O(1) 5979(15)

O(3)-Ru(1)-P(43) 9947(12)

O(1)-Ru(1)-P(43) 15664(11)

O(3)-Ru(1)-P(13) 16018(12)

O(1)-Ru(1)-P(13) 10841(11)

P(43)-Ru(1)-P(13) 9445(6)

O(3)-Ru(1)-P(11) 9159(12)

O(1)-Ru(1)-P(11) 9023(11)

P(43)-Ru(1)-P(11) 10176(6)

P(13)-Ru(1)-P(11) 7170(6)

O(3)-Ru(1)-P(41) 9644(12)

O(1)-Ru(1)-P(41) 9776(11)

P(43)-Ru(1)-P(41) 7245(6)

P(13)-Ru(1)-P(41) 10118(6)

P(11)-Ru(1)-P(41) 17076(6)

O(3)-Ru(1)-C(2) 2985(16)

O(1)-Ru(1)-C(2) 3003(16)

P(43)-Ru(1)-C(2) 12894(14)

P(13)-Ru(1)-C(2) 13584(14)

P(11)-Ru(1)-C(2) 8942(13)

P(41)-Ru(1)-C(2) 9982(13)

C(2)-O(1)-Ru(1) 882(3)

O(3)-C(2)-O(1) 1201(5)

O(3)-C(2)-C(4) 1191(5)

O(1)-C(2)-C(4) 1208(5)

O(3)-C(2)-Ru(1) 586(3)

O(1)-C(2)-Ru(1) 618(3)

C(4)-C(2)-Ru(1) 1735(4)

C(2)-O(3)-Ru(1) 916(4)

C(67)-C(62)-P(43) 1201(5)

C(62)-C(63)-C(64) 1199(6)

C(65)-C(64)-C(63) 1203(7)

C(64)-C(65)-C(66) 1207(6)

C(65)-C(66)-C(67) 1197(6)

C(66)-C(67)-C(62) 1206(6)

C(83)-B(70)-C(77) 1137(6)

C(83)-B(70)-C(89) 1124(6)

C(77)-B(70)-C(89) 1039(6)

C(83)-B(70)-C(71) 1032(6)

C(77)-B(70)-C(71) 1114(6)

C(89)-B(70)-C(71) 1124(6)

C(76)-C(71)-C(72) 1146(7)

C(76)-C(71)-B(70) 1245(7)

C(72)-C(71)-B(70) 1209(7)

C(73)-C(72)-C(71) 1239(8)

C(74)-C(73)-C(72) 1201(9)

C(73)-C(74)-C(75) 1188(8)

C(74)-C(75)-C(76) 1206(9)

C(71)-C(76)-C(75) 1219(8)

C(82)-C(77)-C(78) 1150(7)

C(82)-C(77)-B(70) 1238(7)

C(78)-C(77)-B(70) 1208(7)

C(79)-C(78)-C(77) 1230(8)

C(80)-C(79)-C(78) 1199(9)

C(81)-C(80)-C(79) 1191(9)

C(80)-C(81)-C(82) 1211(8)

C(77)-C(82)-C(81) 1220(8)

C(88)-C(83)-C(84) 1154(8)

C(88)-C(83)-B(70) 1249(8)

C(84)-C(83)-B(70) 1196(8)

C(85)-C(84)-C(83) 1222(10)

C(86)-C(85)-C(84) 1197(10)

C(87)-C(86)-C(85) 1201(10)

C(86)-C(87)-C(88) 1194(11)

C(83)-C(88)-C(87) 1232(10)

C(94)-C(89)-C(90) 1145(7)

C(94)-C(89)-B(70) 1249(6)

C(90)-C(89)-B(70) 1204(7)

C(91)-C(90)-C(89) 1227(8)

C(92)-C(91)-C(90) 1202(8)

C(93)-C(92)-C(91) 1196(9)

C(92)-C(93)-C(94) 1206(8)

C(89)-C(94)-C(93) 1224(8)

Cl(2)-C(100)-Cl(1) 1150(7)

Cl(4)-C(110)-Cl(3) 1199(8)

Cl(5)-C(120)-Cl(6) 1119(9)

208





25(C H2 Cl2)






b = 147789(5) Aring = 73377(3)deg

c = 214417(6) Aring = 75105(3)deg




F(000) 1926







209











Au(1)-P(11) 22545(16)

Au(1)-S(10) 23027(16)

Re(1)-C(83) 1895(7)

Re(1)-C(84) 1915(7)

Re(1)-C(85) 1931(9)

Re(1)-C(85) 1947(7)

Re(1)-N(43) 2161(5)

Re(1)-N(32) 2175(5)

Re(1)-Cl(1) 2271(8)

Re(1)-Cl(1) 2337(4)

Ru(1)-C(82) 1807(6)

Ru(1)-C(30) 2013(5)

Ru(1)-O(1) 2194(3)

Ru(1)-O(3) 2236(4)

Ru(1)-P(63) 23781(16)

Ru(1)-P(44) 23806(17)

Ru(1)-C(2) 2564(5)

C(85)-O(85) 1187(8)

C(85)-O(85) 1178(9)

O(1)-C(2) 1255(7)

C(2)-O(3) 1268(7)

C(2)-C(4) 1480(7)

C(4)-C(9) 1377(8)

C(4)-C(5) 1399(8)

C(5)-C(6) 1360(8)

C(6)-C(7) 1376(8)

C(7)-C(8) 1376(8)

C(7)-S(10) 1761(6)

C(8)-C(9) 1392(8)

P(11)-C(18) 1800(6)

P(11)-C(24) 1811(6)

P(11)-C(12) 1824(6)

C(12)-C(13) 1386(8)

C(12)-C(17) 1388(9)

C(13)-C(14) 1360(10)

C(14)-C(15) 1383(11)

C(15)-C(16) 1395(10)

C(16)-C(17) 1366(9)

C(18)-C(23) 1374(9)

C(18)-C(19) 1405(9)

C(19)-C(20) 1388(9)

C(20)-C(21) 1378(10)

C(21)-C(22) 1346(11)

C(30)-Ru(1)-C(2) 1308(2)

O(1)-Ru(1)-C(2) 2928(16)

O(3)-Ru(1)-C(2) 2965(16)

P(63)-Ru(1)-C(2) 8971(14)

P(44)-Ru(1)-C(2) 8897(14)

O(85)-C(85)-Re(1) 1747(13)

O(85)-C(85)-Re(1) 176(4)

C(2)-O(1)-Ru(1) 919(3)

O(1)-C(2)-O(3) 1194(5)

O(1)-C(2)-C(4) 1223(5)

O(3)-C(2)-C(4) 1183(5)

O(1)-C(2)-Ru(1) 588(3)

O(3)-C(2)-Ru(1) 607(3)

C(4)-C(2)-Ru(1) 1784(4)

C(2)-O(3)-Ru(1) 897(3)

C(9)-C(4)-C(5) 1186(5)

C(9)-C(4)-C(2) 1207(5)

C(5)-C(4)-C(2) 1207(6)

C(6)-C(5)-C(4) 1199(6)

C(5)-C(6)-C(7) 1226(6)

C(8)-C(7)-C(6) 1176(5)

C(8)-C(7)-S(10) 1237(5)

C(6)-C(7)-S(10) 1187(5)

C(7)-C(8)-C(9) 1212(6)

C(4)-C(9)-C(8) 1202(6)

C(7)-S(10)-Au(1) 1059(2)

C(18)-P(11)-C(24) 1048(3)

C(18)-P(11)-C(12) 1061(3)

C(24)-P(11)-C(12) 1055(3)

C(18)-P(11)-Au(1) 1112(2)

C(24)-P(11)-Au(1) 1164(2)

C(12)-P(11)-Au(1) 1120(2)

C(13)-C(12)-C(17) 1192(6)

C(13)-C(12)-P(11) 1191(5)

C(17)-C(12)-P(11) 1217(5)

C(14)-C(13)-C(12) 1206(7)

C(13)-C(14)-C(15) 1207(7)

C(14)-C(15)-C(16) 1188(6)

C(17)-C(16)-C(15) 1204(7)

C(16)-C(17)-C(12) 1203(7)

C(23)-C(18)-C(19) 1183(6)

C(23)-C(18)-P(11) 1231(5)

C(19)-C(18)-P(11) 1186(5)

210

C(22)-C(23) 1422(10)

C(24)-C(25) 1378(9)

C(24)-C(29) 1384(8)

C(25)-C(26) 1368(9)

C(26)-C(27) 1380(10)

C(27)-C(28) 1370(10)

C(28)-C(29) 1387(9)

C(30)-C(31) 1331(7)

C(31)-C(34) 1456(8)

N(32)-C(33) 1326(7)

N(32)-C(37) 1356(7)

C(33)-C(34) 1390(8)

C(34)-C(35) 1399(8)

C(35)-C(36) 1363(8)

C(36)-C(37) 1384(8)

C(37)-C(38) 1482(8)

C(38)-N(43) 1341(7)

C(38)-C(39) 1372(8)

C(39)-C(40) 1386(9)

C(40)-C(41) 1364(9)

C(41)-C(42) 1371(9)

C(42)-N(43) 1347(8)

P(44)-C(45) 1819(7)

P(44)-C(57) 1820(7)

P(44)-C(51) 1830(4)

P(44)-C(51) 1861(15)

C(45)-C(46) 1379(10)

C(45)-C(50) 1385(10)

C(46)-C(47) 1356(10)

C(47)-C(48) 1331(14)

C(48)-C(49) 1359(13)

C(49)-C(50) 1397(11)

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(57)-C(58) 1390(9)

C(57)-C(62) 1396(9)

C(58)-C(59) 1396(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1366(10)

C(61)-C(62) 1401(9)

P(63)-C(70) 1812(7)

P(63)-C(76) 1817(9)

P(63)-C(76) 1831(5)

P(63)-C(64) 1831(6)

C(64)-C(65) 1367(9)

C(64)-C(69) 1379(8)

C(65)-C(66) 1381(9)

C(66)-C(67) 1352(9)

C(67)-C(68) 1382(10)

C(68)-C(69) 1394(8)

C(70)-C(75) 1371(10)

C(20)-C(19)-C(18) 1209(6)

C(21)-C(20)-C(19) 1208(7)

C(22)-C(21)-C(20) 1184(7)

C(21)-C(22)-C(23) 1227(7)

C(18)-C(23)-C(22) 1189(7)

C(25)-C(24)-C(29) 1188(6)

C(25)-C(24)-P(11) 1219(5)

C(29)-C(24)-P(11) 1190(5)

C(26)-C(25)-C(24) 1212(6)

C(25)-C(26)-C(27) 1195(7)

C(28)-C(27)-C(26) 1206(7)

C(27)-C(28)-C(29) 1194(7)

C(24)-C(29)-C(28) 1205(7)

C(31)-C(30)-Ru(1) 1354(5)

C(30)-C(31)-C(34) 1249(6)

C(33)-N(32)-C(37) 1176(5)

C(33)-N(32)-Re(1) 1254(4)

C(37)-N(32)-Re(1) 1168(4)

N(32)-C(33)-C(34) 1257(6)

C(33)-C(34)-C(35) 1148(5)

C(33)-C(34)-C(31) 1212(5)

C(35)-C(34)-C(31) 1239(5)

C(36)-C(35)-C(34) 1211(6)

C(35)-C(36)-C(37) 1194(6)

N(32)-C(37)-C(36) 1213(5)

N(32)-C(37)-C(38) 1151(5)

C(36)-C(37)-C(38) 1235(5)

N(43)-C(38)-C(39) 1214(6)

N(43)-C(38)-C(37) 1151(5)

C(39)-C(38)-C(37) 1234(6)

C(38)-C(39)-C(40) 1208(6)

C(41)-C(40)-C(39) 1172(6)

C(40)-C(41)-C(42) 1201(6)

N(43)-C(42)-C(41) 1226(6)

C(38)-N(43)-C(42) 1179(5)

C(38)-N(43)-Re(1) 1180(4)

C(42)-N(43)-Re(1) 1241(4)

C(45)-P(44)-C(57) 1029(3)

C(45)-P(44)-C(51) 1036(4)

C(57)-P(44)-C(51) 1002(4)

C(45)-P(44)-C(51) 1043(12)

C(57)-P(44)-C(51) 1099(10)

C(45)-P(44)-Ru(1) 1140(2)

C(57)-P(44)-Ru(1) 1181(2)

C(51)-P(44)-Ru(1) 1160(3)

C(51)-P(44)-Ru(1) 1068(12)

C(46)-C(45)-C(50) 1180(7)

C(46)-C(45)-P(44) 1194(6)

C(50)-C(45)-P(44) 1226(6)

C(47)-C(46)-C(45) 1219(8)

C(48)-C(47)-C(46) 1204(9)

C(47)-C(48)-C(49) 1203(8)

C(48)-C(49)-C(50) 1208(9)

C(45)-C(50)-C(49) 1186(8)

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1173(4)

C(56)-C(51)-P(44) 1227(4)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

211

C(70)-C(71) 1386(9)

C(71)-C(72) 1392(12)

C(72)-C(73) 1341(13)

C(73)-C(74) 1368(13)

C(74)-C(75) 1396(11)

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(82)-O(82) 1152(7)

C(83)-O(83) 1152(7)

C(84)-O(84) 1138(8)

P(11)-Au(1)-S(10) 17634(6)

C(83)-Re(1)-C(84) 865(3)

C(83)-Re(1)-C(85) 861(15)

C(84)-Re(1)-C(85) 924(15)

C(83)-Re(1)-C(85) 896(5)

C(84)-Re(1)-C(85) 887(5)

C(83)-Re(1)-N(43) 1003(2)

C(84)-Re(1)-N(43) 1732(2)

C(85)-Re(1)-N(43) 884(14)

C(85)-Re(1)-N(43) 910(5)

C(83)-Re(1)-N(32) 1743(2)

C(84)-Re(1)-N(32) 986(2)

C(85)-Re(1)-N(32) 913(15)

C(85)-Re(1)-N(32) 930(5)

N(43)-Re(1)-N(32) 7463(18)

C(83)-Re(1)-Cl(1) 974(3)

C(84)-Re(1)-Cl(1) 941(3)

C(85)-Re(1)-Cl(1) 1729(14)

N(43)-Re(1)-Cl(1) 848(2)

N(32)-Re(1)-Cl(1) 847(2)

C(83)-Re(1)-Cl(1) 873(3)

C(84)-Re(1)-Cl(1) 926(3)

C(85)-Re(1)-Cl(1) 1766(5)

N(43)-Re(1)-Cl(1) 8805(17)

N(32)-Re(1)-Cl(1) 8998(17)

C(82)-Ru(1)-C(30) 917(3)

C(82)-Ru(1)-O(1) 1667(2)

C(30)-Ru(1)-O(1) 10156(19)

C(82)-Ru(1)-O(3) 1078(2)

C(30)-Ru(1)-O(3) 1604(2)

O(1)-Ru(1)-O(3) 5893(14)

C(82)-Ru(1)-P(63) 8796(19)

C(30)-Ru(1)-P(63) 9106(17)

O(1)-Ru(1)-P(63) 9197(11)

O(3)-Ru(1)-P(63) 8801(11)

C(82)-Ru(1)-P(44) 9536(19)

C(30)-Ru(1)-P(44) 8717(17)

O(1)-Ru(1)-P(44) 8519(11)

O(3)-Ru(1)-P(44) 9255(11)

P(63)-Ru(1)-P(44) 17628(6)

C(55)-C(56)-C(51) 1200

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1203(18)

C(56)-C(51)-P(44) 1196(18)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

C(55)-C(56)-C(51) 1200

C(58)-C(57)-C(62) 1183(6)

C(58)-C(57)-P(44) 1217(6)

C(62)-C(57)-P(44) 1199(5)

C(57)-C(58)-C(59) 1199(8)

C(60)-C(59)-C(58) 1211(8)

C(61)-C(60)-C(59) 1200(7)

C(60)-C(61)-C(62) 1198(7)

C(57)-C(62)-C(61) 1208(7)

C(70)-P(63)-C(76) 1091(6)

C(70)-P(63)-C(76) 1009(4)

C(70)-P(63)-C(64) 1038(3)

C(76)-P(63)-C(64) 1055(7)

C(76)-P(63)-C(64) 1038(5)

C(70)-P(63)-Ru(1) 1150(2)

C(76)-P(63)-Ru(1) 1081(6)

C(76)-P(63)-Ru(1) 1166(4)

C(64)-P(63)-Ru(1) 11489(19)

C(65)-C(64)-C(69) 1180(6)

C(65)-C(64)-P(63) 1231(4)

C(69)-C(64)-P(63) 1189(5)

C(64)-C(65)-C(66) 1216(6)

C(67)-C(66)-C(65) 1204(7)

C(66)-C(67)-C(68) 1196(6)

C(67)-C(68)-C(69) 1195(6)

C(64)-C(69)-C(68) 1208(7)

C(75)-C(70)-C(71) 1178(7)

C(75)-C(70)-P(63) 1200(5)

C(71)-C(70)-P(63) 1221(6)

C(70)-C(71)-C(72) 1205(8)

C(73)-C(72)-C(71) 1195(8)

C(72)-C(73)-C(74) 1225(9)

C(73)-C(74)-C(75) 1173(10)

C(70)-C(75)-C(74) 1223(8)

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1210(6)

C(81)-C(76)-P(63) 1190(6)

C(76)-C(77)-C(78) 1200

C(79)-C(78)-C(77) 1200

C(78)-C(79)-C(80) 1200

C(81)-C(80)-C(79) 1200

C(80)-C(81)-C(76) 1200

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1215(10)

C(81)-C(76)-P(63) 1184(10)

C(78)-C(77)-C(76) 1200

C(77)-C(78)-C(79) 1200

C(80)-C(79)-C(78) 1200

C(79)-C(80)-C(81) 1200

C(80)-C(81)-C(76) 1200

O(82)-C(82)-Ru(1) 1771(5)

O(83)-C(83)-Re(1) 1771(7)

O(84)-C(84)-Re(1) 1793(6)

212

C(82)-Ru(1)-C(2) 1374(2)










b = 155218(4) Aring = 107289(3)deg

c = 268129(9) Aring = 90deg




F(000) 3784






213












Pd(1)-P(2) 22948(10)

Pd(1)-P(1) 23232(10)

Pd(1)-S(3) 23304(10)

Pd(1)-S(1) 23536(10)

Pd(2)-P(4) 22985(10)

Pd(2)-S(12) 23240(10)

Pd(2)-P(3) 23292(10)

Pd(2)-S(10) 23512(10)

P(1)-C(13) 1814(4)

P(1)-C(25) 1815(4)

P(1)-C(19) 1818(4)

P(2)-C(31) 1809(4)

P(2)-C(43) 1810(4)

P(2)-C(37) 1823(4)

P(3)-C(49) 1805(4)

P(3)-C(61) 1822(4)

P(3)-C(55) 1822(4)

P(4)-C(79) 1818(4)

P(4)-C(67) 1821(4)

P(4)-C(73) 1826(4)

S(1)-C(2) 1735(4)

C(2)-N(4) 1302(5)

C(2)-S(3) 1722(4)

N(4)-C(5) 1458(5)

N(4)-C(9) 1478(5)

C(5)-C(6) 1524(6)

C(6)-N(7) 1473(5)

N(7)-C(11) 1308(5)

N(7)-C(8) 1464(5)

C(8)-C(9) 1511(6)

S(10)-C(11) 1728(4)

C(11)-S(12) 1717(4)

C(13)-C(18) 1380(6)

C(13)-C(14) 1383(6)

C(14)-C(15) 1384(7)

C(15)-C(16) 1371(8)

C(16)-C(17) 1341(8)

C(17)-C(18) 1383(7)

C(19)-C(24) 1371(6)

C(19)-C(20) 1392(6)

C(20)-C(21) 1372(7)

C(79)-P(4)-C(73) 9763(18)

C(67)-P(4)-C(73) 1063(2)

C(79)-P(4)-Pd(2) 11555(13)

C(67)-P(4)-Pd(2) 10862(13)

C(73)-P(4)-Pd(2) 11746(14)

C(2)-S(1)-Pd(1) 8607(13)

N(4)-C(2)-S(3) 1232(3)

N(4)-C(2)-S(1) 1256(3)

S(3)-C(2)-S(1) 1112(2)

C(2)-S(3)-Pd(1) 8709(14)

C(2)-N(4)-C(5) 1228(3)

C(2)-N(4)-C(9) 1227(3)

C(5)-N(4)-C(9) 1145(3)

N(4)-C(5)-C(6) 1090(3)

N(7)-C(6)-C(5) 1095(3)

C(11)-N(7)-C(8) 1244(3)

C(11)-N(7)-C(6) 1220(3)

C(8)-N(7)-C(6) 1133(3)

N(7)-C(8)-C(9) 1103(3)

N(4)-C(9)-C(8) 1100(3)

C(11)-S(10)-Pd(2) 8619(13)

N(7)-C(11)-S(12) 1234(3)

N(7)-C(11)-S(10) 1253(3)

S(12)-C(11)-S(10) 1112(2)

C(11)-S(12)-Pd(2) 8729(13)

C(18)-C(13)-C(14) 1183(4)

C(18)-C(13)-P(1) 1234(3)

C(14)-C(13)-P(1) 1183(3)

C(13)-C(14)-C(15) 1211(5)

C(16)-C(15)-C(14) 1195(5)

C(17)-C(16)-C(15) 1194(5)

C(16)-C(17)-C(18) 1223(5)

C(13)-C(18)-C(17) 1192(5)

C(24)-C(19)-C(20) 1199(4)

C(24)-C(19)-P(1) 1194(3)

C(20)-C(19)-P(1) 1207(4)

C(21)-C(20)-C(19) 1199(5)

C(22)-C(21)-C(20) 1206(6)

C(21)-C(22)-C(23) 1211(5)

C(22)-C(23)-C(24) 1187(6)

214

C(21)-C(22) 1342(9)

C(22)-C(23) 1390(9)

C(23)-C(24) 1402(7)

C(25)-C(30) 1390(5)

C(25)-C(26) 1405(5)

C(26)-C(27) 1377(6)

C(27)-C(28) 1380(6)

C(28)-C(29) 1375(6)

C(29)-C(30) 1380(6)

C(31)-C(32) 1390(6)

C(31)-C(36) 1392(6)

C(32)-C(33) 1387(6)

C(33)-C(34) 1380(8)

C(34)-C(35) 1365(8)

C(35)-C(36) 1384(7)

C(37)-C(42) 1379(6)

C(37)-C(38) 1388(6)

C(38)-C(39) 1382(6)

C(39)-C(40) 1367(7)

C(40)-C(41) 1356(7)

C(41)-C(42) 1386(6)

C(43)-C(44) 1381(6)

C(43)-C(48) 1393(6)

C(44)-C(45) 1394(7)

C(45)-C(46) 1373(8)

C(46)-C(47) 1365(8)

C(47)-C(48) 1390(6)

C(49)-C(50) 1388(5)

C(49)-C(54) 1402(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1360(6)

C(52)-C(53) 1384(6)

C(53)-C(54) 1372(6)

C(55)-C(56) 1390(5)

C(55)-C(60) 1393(5)

C(56)-C(57) 1385(6)

C(57)-C(58) 1374(6)

C(58)-C(59) 1375(6)

C(59)-C(60) 1377(6)

C(61)-C(66) 1393(6)

C(61)-C(62) 1394(6)

C(62)-C(63) 1388(6)

C(63)-C(64) 1379(7)

C(64)-C(65) 1373(7)

C(65)-C(66) 1384(6)

C(67)-C(72) 1387(6)

C(67)-C(68) 1387(6)

C(68)-C(69) 1378(6)

C(69)-C(70) 1362(7)

C(70)-C(71) 1375(8)

C(71)-C(72) 1376(7)

C(73)-C(78) 1371(6)

C(73)-C(74) 1392(6)

C(74)-C(75) 1371(7)

C(75)-C(76) 1369(8)

C(76)-C(77) 1376(8)

C(77)-C(78) 1410(6)

C(79)-C(84) 1384(5)

C(79)-C(80) 1394(5)

C(80)-C(81) 1374(6)

C(81)-C(82) 1387(6)

C(19)-C(24)-C(23) 1198(5)

C(30)-C(25)-C(26) 1184(4)

C(30)-C(25)-P(1) 1208(3)

C(26)-C(25)-P(1) 1207(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1200(4)

C(29)-C(28)-C(27) 1201(4)

C(28)-C(29)-C(30) 1205(4)

C(29)-C(30)-C(25) 1204(4)

C(32)-C(31)-C(36) 1193(4)

C(32)-C(31)-P(2) 1192(3)

C(36)-C(31)-P(2) 1214(4)

C(33)-C(32)-C(31) 1204(5)

C(34)-C(33)-C(32) 1195(5)

C(35)-C(34)-C(33) 1205(5)

C(34)-C(35)-C(36) 1207(5)

C(35)-C(36)-C(31) 1196(5)

C(42)-C(37)-C(38) 1188(4)

C(42)-C(37)-P(2) 1230(3)

C(38)-C(37)-P(2) 1180(3)

C(39)-C(38)-C(37) 1200(4)

C(40)-C(39)-C(38) 1204(5)

C(41)-C(40)-C(39) 1201(4)

C(40)-C(41)-C(42) 1204(5)

C(37)-C(42)-C(41) 1203(4)

C(44)-C(43)-C(48) 1202(4)

C(44)-C(43)-P(2) 1243(4)

C(48)-C(43)-P(2) 1154(3)

C(43)-C(44)-C(45) 1192(5)

C(46)-C(45)-C(44) 1201(5)

C(47)-C(46)-C(45) 1211(5)

C(46)-C(47)-C(48) 1196(5)

C(47)-C(48)-C(43) 1198(5)

C(50)-C(49)-C(54) 1191(4)

C(50)-C(49)-P(3) 1196(3)

C(54)-C(49)-P(3) 1212(3)

C(49)-C(50)-C(51) 1197(4)

C(52)-C(51)-C(50) 1202(4)

C(51)-C(52)-C(53) 1209(4)

C(54)-C(53)-C(52) 1197(4)

C(53)-C(54)-C(49) 1204(4)

C(56)-C(55)-C(60) 1185(4)

C(56)-C(55)-P(3) 1219(3)

C(60)-C(55)-P(3) 1193(3)

C(57)-C(56)-C(55) 1200(4)

C(58)-C(57)-C(56) 1208(4)

C(57)-C(58)-C(59) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(59)-C(60)-C(55) 1209(4)

C(66)-C(61)-C(62) 1187(4)

C(66)-C(61)-P(3) 1201(3)

C(62)-C(61)-P(3) 1211(3)

C(63)-C(62)-C(61) 1199(4)

C(64)-C(63)-C(62) 1208(5)

C(65)-C(64)-C(63) 1194(4)

C(64)-C(65)-C(66) 1207(5)

C(65)-C(66)-C(61) 1204(4)

C(72)-C(67)-C(68) 1191(4)

C(72)-C(67)-P(4) 1188(3)

C(68)-C(67)-P(4) 1215(3)

C(69)-C(68)-C(67) 1199(5)

215

C(82)-C(83) 1375(6)

C(83)-C(84) 1368(5)

P(10)-F(13) 1549(4)

P(10)-F(15) 1560(4)

P(10)-F(14) 1560(3)

P(10)-F(12) 1564(4)

P(10)-F(11) 1582(3)

P(10)-F(16) 1592(3)

P(20)-F(23) 1557(3)

P(20)-F(21) 1565(3)

P(20)-F(26) 1573(3)

P(20)-F(24) 1582(3)

P(20)-F(22) 1584(3)

P(20)-F(25) 1589(3)

O(90)-C(91) 1361(6)

O(90)-C(93) 1397(7)

C(91)-C(92) 1483(8)

C(93)-C(94) 1393(8)

O(90)-C(91) 1341(10)

O(90)-C(93) 1345(10)

C(91)-C(92) 1452(10)

C(93)-C(94) 1451(10)

P(2)-Pd(1)-P(1) 10098(4)

P(2)-Pd(1)-S(3) 16943(4)

P(1)-Pd(1)-S(3) 8822(4)

P(2)-Pd(1)-S(1) 9507(4)

P(1)-Pd(1)-S(1) 16140(4)

S(3)-Pd(1)-S(1) 7504(4)

P(4)-Pd(2)-S(12) 17025(4)

P(4)-Pd(2)-P(3) 10004(4)

S(12)-Pd(2)-P(3) 8970(3)

P(4)-Pd(2)-S(10) 9535(3)

S(12)-Pd(2)-S(10) 7490(3)

P(3)-Pd(2)-S(10) 16452(4)

C(13)-P(1)-C(25) 10983(18)

C(13)-P(1)-C(19) 1033(2)

C(25)-P(1)-C(19) 10175(19)

C(13)-P(1)-Pd(1) 10736(14)

C(25)-P(1)-Pd(1) 10878(12)

C(19)-P(1)-Pd(1) 12519(13)

C(31)-P(2)-C(43) 10980(19)

C(31)-P(2)-C(37) 10173(17)

C(43)-P(2)-C(37) 10461(19)

C(31)-P(2)-Pd(1) 11826(15)

C(43)-P(2)-Pd(1) 10682(14)

C(37)-P(2)-Pd(1) 11481(13)

C(49)-P(3)-C(61) 10500(18)

C(49)-P(3)-C(55) 10370(18)

C(61)-P(3)-C(55) 10515(18)

C(49)-P(3)-Pd(2) 11419(12)

C(61)-P(3)-Pd(2) 11999(13)

C(55)-P(3)-Pd(2) 10732(12)

C(79)-P(4)-C(67) 11063(18)

C(70)-C(69)-C(68) 1209(5)

C(69)-C(70)-C(71) 1194(5)

C(70)-C(71)-C(72) 1209(5)

C(71)-C(72)-C(67) 1197(5)

C(78)-C(73)-C(74) 1201(4)

C(78)-C(73)-P(4) 1194(3)

C(74)-C(73)-P(4) 1189(3)

C(75)-C(74)-C(73) 1205(5)

C(76)-C(75)-C(74) 1197(5)

C(75)-C(76)-C(77) 1209(5)

C(76)-C(77)-C(78) 1196(5)

C(73)-C(78)-C(77) 1191(5)

C(84)-C(79)-C(80) 1198(4)

C(84)-C(79)-P(4) 1151(3)

C(80)-C(79)-P(4) 1246(3)

C(81)-C(80)-C(79) 1192(4)

C(80)-C(81)-C(82) 1206(4)

C(83)-C(82)-C(81) 1199(4)

C(84)-C(83)-C(82) 1201(4)

C(83)-C(84)-C(79) 1205(4)

F(13)-P(10)-F(15) 1779(3)

F(13)-P(10)-F(14) 913(3)

F(15)-P(10)-F(14) 902(3)

F(13)-P(10)-F(12) 903(3)

F(15)-P(10)-F(12) 882(3)

F(14)-P(10)-F(12) 1775(3)

F(13)-P(10)-F(11) 914(2)

F(15)-P(10)-F(11) 901(2)

F(14)-P(10)-F(11) 915(2)

F(12)-P(10)-F(11) 903(2)

F(13)-P(10)-F(16) 891(2)

F(15)-P(10)-F(16) 8948(19)

F(14)-P(10)-F(16) 8896(18)

F(12)-P(10)-F(16) 892(2)

F(11)-P(10)-F(16) 1793(2)

F(23)-P(20)-F(21) 896(2)

F(23)-P(20)-F(26) 923(2)

F(21)-P(20)-F(26) 1778(2)

F(23)-P(20)-F(24) 9177(19)

F(21)-P(20)-F(24) 8826(17)

F(26)-P(20)-F(24) 9056(16)

F(23)-P(20)-F(22) 893(2)

F(21)-P(20)-F(22) 9091(19)

F(26)-P(20)-F(22) 9024(18)

F(24)-P(20)-F(22) 1787(2)

F(23)-P(20)-F(25) 1794(2)

F(21)-P(20)-F(25) 908(2)

F(26)-P(20)-F(25) 873(2)

F(24)-P(20)-F(25) 8868(19)

F(22)-P(20)-F(25) 903(2)

C(91)-O(90)-C(93) 1125(6)

O(90)-C(91)-C(92) 1100(6)

C(94)-C(93)-O(90) 1137(7)

C(91)-O(90)-C(93) 119(2)

O(90)-C(91)-C(92) 1157(17)

O(90)-C(93)-C(94) 1167(17)

216










b = 107032(4) Aring = 78500(4)deg

c = 212565(12) Aring = 88333(3)deg




F(000) 946









217









Pd(1)-P(2) 22888(9)

Pd(1)-P(1) 23146(9)

Pd(1)-S(1) 23388(8)

Pd(1)-S(3) 23479(9)

P(1)-C(7) 1816(4)

P(1)-C(13) 1817(3)

P(1)-C(19) 1825(4)

P(2)-C(25) 1809(4)

P(2)-C(37) 1821(4)

P(2)-C(31) 1822(4)

S(1)-C(2) 1727(4)

C(2)-N(4) 1326(4)

C(2)-S(3) 1714(4)

N(4)-C(5) 1463(5)

N(4)-C(6) 1480(5)

C(5)-C(6)1 1519(6)

C(6)-C(5)1 1519(6)

C(7)-C(8) 1398(6)

C(7)-C(12) 1399(5)

C(8)-C(9) 1378(6)

C(9)-C(10) 1379(7)

C(10)-C(11) 1390(8)

C(11)-C(12) 1369(7)

C(13)-C(14) 1386(6)

C(13)-C(18) 1392(5)

C(14)-C(15) 1389(5)

C(15)-C(16) 1380(6)

C(16)-C(17) 1381(7)

C(17)-C(18) 1397(5)

C(19)-C(24) 1383(6)

C(19)-C(20) 1386(6)

C(20)-C(21) 1388(6)

C(21)-C(22) 1375(8)

C(22)-C(23) 1370(9)

C(23)-C(24) 1407(7)

C(25)-C(30) 1394(6)

C(25)-C(26) 1396(6)

C(26)-C(27) 1379(6)

C(27)-C(28) 1384(8)

C(28)-C(29) 1365(8)

C(29)-C(30) 1395(6)

C(31)-C(32) 1389(5)

C(31)-C(36) 1391(5)

C(32)-C(33) 1392(6)

C(33)-C(34) 1377(7)

C(34)-C(35) 1377(6)

C(8)-C(7)-P(1) 1204(3)

C(12)-C(7)-P(1) 1209(3)

C(9)-C(8)-C(7) 1203(4)

C(8)-C(9)-C(10) 1202(5)

C(9)-C(10)-C(11) 1199(5)

C(12)-C(11)-C(10) 1202(4)

C(11)-C(12)-C(7) 1205(4)

C(14)-C(13)-C(18) 1191(3)

C(14)-C(13)-P(1) 1215(3)

C(18)-C(13)-P(1) 1194(3)

C(13)-C(14)-C(15) 1204(4)

C(16)-C(15)-C(14) 1202(4)

C(15)-C(16)-C(17) 1202(4)

C(16)-C(17)-C(18) 1196(4)

C(13)-C(18)-C(17) 1204(4)

C(24)-C(19)-C(20) 1194(4)

C(24)-C(19)-P(1) 1224(3)

C(20)-C(19)-P(1) 1182(3)

C(19)-C(20)-C(21) 1209(5)

C(22)-C(21)-C(20) 1197(5)

C(23)-C(22)-C(21) 1201(5)

C(22)-C(23)-C(24) 1207(5)

C(19)-C(24)-C(23) 1192(5)

C(30)-C(25)-C(26) 1191(4)

C(30)-C(25)-P(2) 1230(3)

C(26)-C(25)-P(2) 1176(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1197(5)

C(29)-C(28)-C(27) 1206(4)

C(28)-C(29)-C(30) 1204(5)

C(25)-C(30)-C(29) 1196(4)

C(32)-C(31)-C(36) 1189(4)

C(32)-C(31)-P(2) 1257(3)

C(36)-C(31)-P(2) 1153(3)

C(31)-C(32)-C(33) 1198(4)

C(34)-C(33)-C(32) 1207(4)

C(35)-C(34)-C(33) 1198(4)

C(34)-C(35)-C(36) 1200(4)

C(35)-C(36)-C(31) 1207(4)

C(42)-C(37)-C(38) 1184(4)

C(42)-C(37)-P(2) 1189(3)

C(38)-C(37)-P(2) 1227(3)

C(39)-C(38)-C(37) 1197(5)

C(40)-C(39)-C(38) 1206(5)

C(39)-C(40)-C(41) 1208(5)

C(40)-C(41)-C(42) 1197(5)

218

C(35)-C(36) 1387(6)

C(37)-C(42) 1385(6)

C(37)-C(38) 1399(6)

C(38)-C(39) 1392(6)

C(39)-C(40) 1360(8)

C(40)-C(41) 1361(8)

C(41)-C(42) 1394(7)

P(10)-F(14) 1578(10)

P(10)-F(13) 1579(10)

P(10)-F(16) 1597(10)

P(10)-F(12) 1598(10)

P(10)-F(15) 1599(10)

P(10)-F(11) 1614(10)

P(10)-F(11) 1588(13)

P(10)-F(13) 1591(13)

P(10)-F(14) 1592(13)

P(10)-F(12) 1593(13)

P(10)-F(16) 1595(13)

P(10)-F(15) 1598(13)

P(20)-F(25) 1551(11)

P(20)-F(24) 1557(12)

P(20)-F(26) 1563(11)

P(20)-F(22) 1566(11)

P(20)-F(21) 1575(11)

P(20)-F(23) 1585(11)

P(20)-F(23) 1521(11)

P(20)-F(21) 1545(11)

P(20)-F(26) 1559(11)

P(20)-F(24) 1560(11)

P(20)-F(22) 1585(11)

P(20)-F(25) 1628(11)

P(2)-Pd(1)-P(1) 9715(3)

P(2)-Pd(1)-S(1) 9505(3)

P(1)-Pd(1)-S(1) 16705(3)

P(2)-Pd(1)-S(3) 16837(3)

P(1)-Pd(1)-S(3) 9298(3)

S(1)-Pd(1)-S(3) 7536(3)

C(7)-P(1)-C(13) 10326(17)

C(7)-P(1)-C(19) 10743(19)

C(13)-P(1)-C(19) 10434(17)

C(7)-P(1)-Pd(1) 11069(13)

C(13)-P(1)-Pd(1) 12157(12)

C(19)-P(1)-Pd(1) 10864(13)

C(25)-P(2)-C(37) 10169(18)

C(25)-P(2)-C(31) 11326(17)

C(37)-P(2)-C(31) 10528(17)

C(25)-P(2)-Pd(1) 11377(13)

C(37)-P(2)-Pd(1) 11311(12)

C(31)-P(2)-Pd(1) 10929(13)

C(2)-S(1)-Pd(1) 8589(12)

N(4)-C(2)-S(3) 1233(3)

N(4)-C(2)-S(1) 1239(3)

S(3)-C(2)-S(1) 11276(19)

C(2)-S(3)-Pd(1) 8590(13)

C(2)-N(4)-C(5) 1234(3)

C(2)-N(4)-C(6) 1228(3)

C(5)-N(4)-C(6) 1133(3)

N(4)-C(5)-C(6)1 1090(3)

N(4)-C(6)-C(5)1 1087(3)

C(8)-C(7)-C(12) 1188(4)

C(37)-C(42)-C(41) 1208(4)

F(14)-P(10)-F(13) 910(7)

F(14)-P(10)-F(16) 912(6)

F(13)-P(10)-F(16) 912(6)

F(14)-P(10)-F(12) 1781(8)

F(13)-P(10)-F(12) 901(7)

F(16)-P(10)-F(12) 904(7)

F(14)-P(10)-F(15) 902(7)

F(13)-P(10)-F(15) 1783(8)

F(16)-P(10)-F(15) 901(7)

F(12)-P(10)-F(15) 886(7)

F(14)-P(10)-F(11) 901(7)

F(13)-P(10)-F(11) 894(7)

F(16)-P(10)-F(11) 1785(9)

F(12)-P(10)-F(11) 883(6)

F(15)-P(10)-F(11) 893(6)

F(11)-P(10)-F(13) 904(8)

F(11)-P(10)-F(14) 902(8)

F(13)-P(10)-F(14) 903(8)

F(11)-P(10)-F(12) 902(8)

F(13)-P(10)-F(12) 901(8)

F(14)-P(10)-F(12) 1795(11)

F(11)-P(10)-F(16) 1794(11)

F(13)-P(10)-F(16) 902(8)

F(14)-P(10)-F(16) 899(8)

F(12)-P(10)-F(16) 897(8)

F(11)-P(10)-F(15) 898(8)

F(13)-P(10)-F(15) 1798(12)

F(14)-P(10)-F(15) 899(8)

F(12)-P(10)-F(15) 897(8)

F(16)-P(10)-F(15) 896(8)

F(25)-P(20)-F(24) 911(7)

F(25)-P(20)-F(26) 923(7)

F(24)-P(20)-F(26) 911(7)

F(25)-P(20)-F(22) 916(7)

F(24)-P(20)-F(22) 1766(10)

F(26)-P(20)-F(22) 908(7)

F(25)-P(20)-F(21) 899(7)

F(24)-P(20)-F(21) 902(8)

F(26)-P(20)-F(21) 1774(9)

F(22)-P(20)-F(21) 878(7)

F(25)-P(20)-F(23) 1786(10)

F(24)-P(20)-F(23) 894(7)

F(26)-P(20)-F(23) 890(7)

F(22)-P(20)-F(23) 879(7)

F(21)-P(20)-F(23) 888(7)

F(23)-P(20)-F(21) 941(7)

F(23)-P(20)-F(26) 932(7)

F(21)-P(20)-F(26) 1724(8)

F(23)-P(20)-F(24) 939(7)

F(21)-P(20)-F(24) 907(7)

F(26)-P(20)-F(24) 910(7)

F(23)-P(20)-F(22) 931(7)

F(21)-P(20)-F(22) 887(7)

F(26)-P(20)-F(22) 886(7)

F(24)-P(20)-F(22) 1730(8)

F(23)-P(20)-F(25) 1771(9)

F(21)-P(20)-F(25) 878(7)

F(26)-P(20)-F(25) 849(7)

F(24)-P(20)-F(25) 883(7)

F(22)-P(20)-F(25) 847(6)

219










b = 1085381(18) Aring = 1065109(16)deg

c = 267343(4) Aring = 90deg




F(000) 4112








220











Pd(1)-P(2) 22811(15)

Pd(1)-S(1) 23190(15)

Pd(1)-P(1) 23297(15)

Pd(1)-S(3) 23720(16)

Pd(2)-P(4) 22915(17)

Pd(2)-S(9) 23180(15)

Pd(2)-P(3) 23298(16)

Pd(2)-S(10) 23735(17)

P(1)-C(37) 1820(7)

P(1)-C(25) 1826(7)

P(1)-C(31) 1832(7)

P(2)-C(43) 1814(6)

P(2)-C(49) 1820(6)

P(2)-C(55) 1826(7)

P(3)-C(61) 1832(9)

P(3)-C(67) 1832(7)

P(3)-C(73) 1837(7)

P(4)-C(85) 1815(7)

P(4)-C(79) 1829(7)

P(4)-C(91) 1833(6)

S(1)-C(2) 1715(7)

C(2)-N(4) 1323(8)

C(2)-S(3) 1718(6)

N(4)-C(5) 1470(8)

N(4)-C(11) 1475(8)

C(5)-C(6) 1518(8)

C(6)-N(7) 1487(8)

N(7)-C(8) 1316(9)

N(7)-C(18) 1463(9)

C(8)-S(9) 1722(7)

C(8)-S(10) 1727(7)

C(11)-C(12) 1500(9)

C(12)-C(13) 1376(11)

C(12)-C(17) 1378(10)

C(13)-C(14) 1385(12)

C(14)-C(15) 1393(14)

C(15)-C(16) 1363(14)

C(16)-C(17) 1377(13)

C(18)-C(19) 1510(11)

C(19)-C(24) 1374(12)

C(19)-C(20) 1406(11)

C(20)-C(21) 1390(15)

C(21)-C(22) 1352(18)

C(22)-C(23) 1395(16)

C(79)-P(4)-Pd(2) 1116(2)

C(91)-P(4)-Pd(2) 1124(20

C(2)-S(1)-Pd(1) 859(2)

N(4)-C(2)-S(1) 1227(5)

N(4)-C(2)-S(3) 1240(5)

S(1)-C(2)-S(3) 1132(4)

C(2)-S(3)-Pd(1) 842(2)

C(2)-N(4)-C(5) 1214(5)

C(2)-N(4)-C(11) 1207(5)

C(5)-N(4)-C(11) 1176(5)

N(4)-C(5)-C(6) 1104(5)

N(7)-C(6)-C(5) 1085(5)

C(8)-N(7)-C(18) 1229(6)

C(8)-N(7)-C(6) 1194(6)

C(18)-N(7)-C(6) 1177(5)

N(7)-C(8)-S(9) 1234(5)

N(7)-C(8)-S(10) 1247(5)

S(9)-C(8)-S(10) 1119(4)

C(8)-S(9)-Pd(2) 873(2)

C(8)-S(10)-Pd(2) 854(2)

N(4)-C(11)-C(12) 1154(5)

C(13)-C(12)-C(17) 1187(7)

C(13)-C(12)-C(11) 1218(6)

C(17)-C(12)-C(11) 1193(6)

C(12)-C(13)-C(14) 1206(8)

C(13)-C(14)-C(15) 1203(9)

C(16)-C(15)-C(14) 1185(8)

C(15)-C(16)-C(17) 1214(8)

C(16)-C(17)-C(12) 1206(8)

N(7)-C(18)-C(19) 1127(6)

C(24)-C(19)-C(20) 1180(8)

C(24)-C(19)-C(18) 1234(7)

C(20)-C(19)-C(18) 1185(8)

C(21)-C(20)-C(19) 1189(10)

C(22)-C(21)-C(20) 1229(9)

C(21)-C(22)-C(23) 1187(10)

C(24)-C(23)-C(22) 1193(10)

C(19)-C(24)-C(23) 1222(8)

C(30)-C(25)-C(26) 1194(6)

C(30)-C(25)-P(1) 1211(5)

C(26)-C(25)-P(1) 1194(5)

C(27)-C(26)-C(25) 1195(7)

C(28)-C(27)-C(26) 1206(7)

221

C(23)-C(24) 1389(12)

C(25)-C(30) 1387(10)

C(25)-C(26) 1396(9)

C(26)-C(27) 1392(10)

C(27)-C(28) 1372(12)

C(28)-C(29) 1373(12)

C(29)-C(30) 1391(10)

C(31)-C(32) 1392(9)

C(31)-C(36) 1404(9)

C(32)-C(33) 1390(10)

C(33)-C(34) 1390(13)

C(34)-C(35) 1368(13)

C(35)-C(36) 1396(11)

C(37)-C(42) 1387(10)

C(37)-C(38) 1393(10)

C(38)-C(39) 1387(10)

C(39)-C(40) 1361(12)

C(40)-C(41) 1385(12)

C(41)-C(42) 1390(10)

C(43)-C(48) 1396(10)

C(43)-C(44) 1400(10)

C(44)-C(45) 1370(10)

C(45)-C(46) 1379(12)

C(46)-C(47) 1382(13)

C(47)-C(48) 1400(11)

C(49)-C(54) 1384(11)

C(49)-C(50) 1400(10)

C(50)-C(51) 1380(9)

C(51)-C(52) 1377(14)

C(52)-C(53) 1362(15)

C(53)-C(54) 1399(11)

C(55)-C(60) 1380(9)

C(55)-C(56) 1407(9)

C(56)-C(57) 1370(10)

C(57)-C(58) 1381(11)

C(58)-C(59) 1402(12)

C(59)-C(60) 1373(11)

C(61)-C(62) 1375(11)

C(61)-C(66) 1404(11)

C(62)-C(63) 1395(11)

C(63)-C(64) 1402(14)

C(64)-C(65) 1358(16)

C(65)-C(66) 1377(14)

C(67)-C(68) 1379(11)

C(67)-C(72) 1401(11)

C(68)-C(69) 1386(11)

C(69)-C(70) 1394(14)

C(70)-C(71) 1376(15)

C(71)-C(72) 1391(12)

C(73)-C(78) 1391(11)

C(73)-C(74) 1400(9)

C(74)-C(75) 1393(13)

C(75)-C(76) 1391(14)

C(76)-C(77) 1394(12)

C(77)-C(78) 1384(13)

C(79)-C(84) 1376(11)

C(79)-C(80) 1402(10)

C(80)-C(81) 1399(10)

C(81)-C(82) 1371(13)

C(82)-C(83) 1384(12)

C(83)-C(84) 1379(10)

C(27)-C(28)-C(29) 1202(7)

C(28)-C(29)-C(30) 1202(7)

C(25)-C(30)-C(29) 1201(7)

C(32)-C(31)-C(36) 1189(6)

C(32)-C(31)-P(1) 1203(5)

C(36)-C(31)-P(1) 1208(5)

C(33)-C(32)-C(31) 1208(7)

C(32)-C(33)-C(34) 1204(7)

C(35)-C(34)-C(33) 1187(7)

C(34)-C(35)-C(36) 1224(7)

C(35)-C(36)-C(31) 1188(7)

C(42)-C(37)-C(38) 1181(6)

C(42)-C(37)-P(1) 1194(5)

C(38)-C(37)-P(1) 1224(5)

C(39)-C(38)-C(37) 1210(7)

C(40)-C(39)-C(38) 1202(7)

C(39)-C(40)-C(41) 1200(7)

C(40)-C(41)-C(42) 1200(7)

C(37)-C(42)-C(41) 1206(7)

C(48)-C(43)-C(44) 1199(6)

C(48)-C(43)-P(2) 1250(6)

C(44)-C(43)-P(2) 1151(5)

C(45)-C(44)-C(43) 1201(7)

C(44)-C(45)-C(46) 1205(7)

C(45)-C(46)-C(47) 1202(7)

C(46)-C(47)-C(48) 1204(7)

C(43)-C(48)-C(47) 1189(8)

C(54)-C(49)-C(50) 1205(6)

C(54)-C(49)-P(2) 1209(6)

C(50)-C(49)-P(2) 1185(5)

C(51)-C(50)-C(49) 1197(7)

C(52)-C(51)-C(50) 1198(8)

C(53)-C(52)-C(51) 1205(7)

C(52)-C(53)-C(54) 1213(8)

C(49)-C(54)-C(53) 1181(8)

C(60)-C(55)-C(56) 1188(6)

C(60)-C(55)-P(2) 1235(5)

C(56)-C(55)-P(2) 1177(5)

C(57)-C(56)-C(55) 1198(6)

C(56)-C(57)-C(58) 1213(7)

C(57)-C(58)-C(59) 1190(7)

C(60)-C(59)-C(58) 1197(7)

C(59)-C(60)-C(55) 1213(7)

C(62)-C(61)-C(66) 1196(8)

C(62)-C(61)-P(3) 1193(6)

C(66)-C(61)-P(3) 1208(7)

C(61)-C(62)-C(63) 1218(8)

C(62)-C(63)-C(64) 1176(9)

C(65)-C(64)-C(63) 1203(8)

C(64)-C(65)-C(66) 1224(9)

C(65)-C(66)-C(61) 1183(9)

C(68)-C(67)-C(72) 1195(7)

C(68)-C(67)-P(3) 1198(6)

C(72)-C(67)-P(3) 1204(6)

C(67)-C(68)-C(69) 1210(8)

C(68)-C(69)-C(70) 1192(8)

C(71)-C(70)-C(69) 1205(8)

C(70)-C(71)-C(72) 1202(9)

C(71)-C(72)-C(67) 1196(9)

C(78)-C(73)-C(74) 1186(7)

C(78)-C(73)-P(3) 1212(5)

222

C(85)-C(90) 1379(11)

C(85)-C(86) 1391(10)

C(86)-C(87) 1391(10)

C(87)-C(88) 1387(15)

C(88)-C(89) 1371(14)

C(89)-C(90) 1390(11)

C(91)-C(92) 1379(9)

C(91)-C(96) 1387(9)

C(92)-C(93) 1393(11)

C(93)-C(94) 1368(12)

C(94)-C(95) 1397(11)

C(95)-C(96) 1375(10)

P(10)-F(11) 1550(6)

P(10)-F(15) 1576(5)

P(10)-F(13) 1584(6)

P(10)-F(14) 1590(6)

P(10)-F(12) 1600(5)

P(10)-F(16) 1600(7)

P(20)-F(26) 1543(8)

P(20)-F(21) 1565(8)

P(20)-F(25) 1565(5)

P(20)-F(22) 1568(6)

P(20)-F(24) 1571(6)

P(20)-F(23) 1581(5)

P(2)-Pd(1)-S(1) 9072(5)

P(2)-Pd(1)-P(1) 9793(6)

S(1)-Pd(1)-P(1) 16824(5)

P(2)-Pd(1)-S(3) 16550(6)

S(1)-Pd(1)-S(3) 7528(5)

P(1)-Pd(1)-S(3) 9647(5)

P(4)-Pd(2)-S(9) 9136(5)

P(4)-Pd(2)-P(3) 9795(6)

S(9)-Pd(2)-P(3) 17015(6)

P(4)-Pd(2)-S(10) 16641(6)

S(9)-Pd(2)-S(10) 7505(5)

P(3)-Pd(2)-S(10) 9564(6)

C(37)-P(1)-C(25) 1061(3)

C(37)-P(1)-C(31) 1040(3)

C(25)-P(1)-C(31) 1013(3)

C(37)-P(1)-Pd(1) 1142(2)

C(25)-P(1)-Pd(1) 1091(2)

C(31)-P(1)-Pd(1) 1205(2)

C(43)-P(2)-C(49) 1115(3)

C(43)-P(2)-C(55) 1047(3)

C(49)-P(2)-C(55) 1020(3)

C(43)-P(2)-Pd(1) 1110(2)

C(49)-P(2)-Pd(1) 1132(2)

C(55)-P(2)-Pd(1) 1139(2)

C(61)-P(3)-C(67) 1067(4)

C(61)-P(3)-C(73) 1028(4)

C(67)-P(3)-C(73) 1047(4)

C(61)-P(3)-Pd(2) 1087(3)

C(67)-P(3)-Pd(2) 1122(3)

C(73)-P(3)-Pd(2) 1207(2)

C(85)-P(4)-C(79) 1107(3)

C(85)-P(4)-C(91) 1023(3)

C(79)-P(4)-C(91) 1052(3)

C(85)-P(4)-Pd(2) 1139(3)

C(74)-C(73)-P(3) 1202(6)

C(75)-C(74)-C(73) 1202(8)

C(76)-C(75)-C(74) 1199(7)

C(75)-C(76)-C(77) 1207(8)

C(78)-C(77)-C(76) 1186(9)

C(77)-C(78)-C(73) 1220(7)

C(84)-C(79)-C(80) 1205(6)

C(84)-C(79)-P(4) 1249(5)

C(80)-C(79)-P(4) 1146(5)

C(81)-C(80)-C(79) 1181(7)

C(82)-C(81)-C(80) 1211(7)

C(81)-C(82)-C(83) 1197(7)

C(84)-C(83)-C(82) 1203(7)

C(79)-C(84)-C(83) 1201(7)

C(90)-C(85)-C(86) 1198(7)

C(90)-C(85)-P(4) 1219(6)

C(86)-C(85)-P(4) 1183(6)

C(87)-C(86)-C(85) 1201(8)

C(88)-C(87)-C(86) 1198(8)

C(89)-C(88)-C(87) 1195(7)

C(88)-C(89)-C(90) 1212(9)

C(85)-C(90)-C(89) 1195(8)

C(92)-C(91)-C(96) 1197(6)

C(92)-C(91)-P(4) 1225(5)

C(96)-C(91)-P(4) 1177(5)

C(91)-C(92)-C(93) 1198(7)

C(94)-C(93)-C(92) 1209(7)

C(93)-C(94)-C(95) 1189(7)

C(96)-C(95)-C(94) 1207(7)

C(95)-C(96)-C(91) 1201(6)

F(11)-P(10)-F(15) 920(4)

F(11)-P(10)-F(13) 909(4)

F(15)-P(10)-F(13) 1769(4)

F(11)-P(10)-F(14) 909(4)

F(15)-P(10)-F(14) 889(3)

F(13)-P(10)-F(14) 921(4)

F(11)-P(10)-F(12) 902(4)

F(15)-P(10)-F(12) 897(3)

F(13)-P(10)-F(12) 892(3)

F(14)-P(10)-F(12) 1783(3)

F(11)-P(10)-F(16) 1792(4)

F(15)-P(10)-F(16) 885(4)

F(13)-P(10)-F(16) 885(4)

F(14)-P(10)-F(16) 897(4)

F(12)-P(10)-F(16) 892(3)

F(26)-P(20)-F(21) 1790(6)

F(26)-P(20)-F(25) 893(5)

F(21)-P(20)-F(25) 897(5)

F(26)-P(20)-F(22) 932(6)

F(21)-P(20)-F(22) 865(6)

F(25)-P(20)-F(22) 894(4)

F(26)-P(20)-F(24) 875(6)

F(21)-P(20)-F(24) 928(6)

F(25)-P(20)-F(24) 907(3)

F(22)-P(20)-F(24) 1794(6)

F(26)-P(20)-F(23) 889(4)

F(21)-P(20)-F(23) 921(4)

F(25)-P(20)-F(23) 1780(5)

F(22)-P(20)-F(23) 899(3)

F(24)-P(20)-F(23) 901(3)

223





224




05(C H2 Cl2)






b = 192506(5) Aring = 970520(16)deg

c = 494978(9) Aring = 90deg




F(000) 8880
















225


Pd(1A)-P(2A) 23045(9)

Pd(1A)-P(1A) 23091(9)

Pd(1A)-S(1A) 23294(9)

Pd(1A)-S(3A) 23458(9)

P(1A)-C(22A) 1817(3)

P(1A)-C(28A) 1820(3)

P(1A)-C(16A) 1821(3)

P(1A)-C(22) 1838(8)

P(2A)-C(46A) 1815(4)

P(2A)-C(34A) 1823(4)

P(2A)-C(40A) 1837(4)

P(2A)-C(40) 1843(6)

S(1A)-C(2A) 1726(3)

C(2A)-N(4A) 1306(4)

C(2A)-S(3A) 1717(4)

N(4A)-C(5A) 1467(5)

N(4A)-C(15A) 1467(4)

C(5A)-C(6A) 1528(5)

C(6A)-C(7A) 1512(5)

C(7A)-Si(8A) 1718(5)

C(7A)-Si(8) 2004(6)

Si(8A)-O(13A) 1602(5)

Si(8A)-O(9A) 1629(6)

Si(8A)-O(11A) 1634(5)

O(9A)-C(10A) 1436(8)

O(11A)-C(12A) 1401(8)

O(13A)-C(14A) 1388(9)

Si(8)-O(9) 1606(8)

Si(8)-O(11) 1618(8)

Si(8)-O(13) 1633(8)

O(9)-C(10) 1422(12)

O(11)-C(12) 1418(13)

O(13)-C(14) 1462(12)

C(16A)-C(21A) 1387(5)

C(16A)-C(17A) 1391(5)

C(17A)-C(18A) 1379(5)

C(18A)-C(19A) 1378(6)

C(19A)-C(20A) 1359(6)

C(20A)-C(21A) 1395(5)

C(22A)-C(23A) 13900

C(22A)-C(27A) 13900

C(23A)-C(24A) 13900

C(24A)-C(25A) 13900

C(25A)-C(26A) 13900

C(26A)-C(27A) 13900

C(22)-C(23) 13900

C(22)-C(27) 13900

C(23)-C(24) 13900

C(24)-C(25) 13900

C(25)-C(26) 13900

C(26)-C(27) 13900

C(28A)-C(33A) 1385(5)

C(28A)-C(29A) 1395(5)

C(29A)-C(30A) 1377(5)

C(30A)-C(31A) 1367(6)

C(31A)-C(32A) 1380(6)

C(32A)-C(33A) 1387(5)

C(34A)-C(35A) 1377(5)

C(34A)-C(39A) 1394(5)

O(13)-Si(8)-C(7A) 1101(4)

C(10)-O(9)-Si(8) 1212(8)

C(12)-O(11)-Si(8) 1233(9)

C(14)-O(13)-Si(8) 1224(8)

C(21A)-C(16A)-C(17A) 1189(3)

C(21A)-C(16A)-P(1A) 1232(3)

C(17A)-C(16A)-P(1A) 1178(3)

C(18A)-C(17A)-C(16A) 1206(4)

C(19A)-C(18A)-C(17A) 1198(4)

C(20A)-C(19A)-C(18A) 1205(4)

C(19A)-C(20A)-C(21A) 1203(4)

C(16A)-C(21A)-C(20A) 1198(4)

C(23A)-C(22A)-C(27A) 1200

C(23A)-C(22A)-P(1A) 1187(3)

C(27A)-C(22A)-P(1A) 1213(3)

C(24A)-C(23A)-C(22A) 1200

C(25A)-C(24A)-C(23A) 1200

C(24A)-C(25A)-C(26A) 1200

C(27A)-C(26A)-C(25A) 1200

C(26A)-C(27A)-C(22A) 1200

C(23)-C(22)-C(27) 1200

C(23)-C(22)-P(1A) 1215(7)

C(27)-C(22)-P(1A) 1185(7)

C(24)-C(23)-C(22) 1200

C(25)-C(24)-C(23) 1200

C(24)-C(25)-C(26) 1200

C(25)-C(26)-C(27) 1200

C(26)-C(27)-C(22) 1200

C(33A)-C(28A)-C(29A) 1187(3)

C(33A)-C(28A)-P(1A) 1220(3)

C(29A)-C(28A)-P(1A) 1193(3)

C(30A)-C(29A)-C(28A) 1205(4)

C(31A)-C(30A)-C(29A) 1205(4)

C(30A)-C(31A)-C(32A) 1199(4)

C(31A)-C(32A)-C(33A) 1202(4)

C(28A)-C(33A)-C(32A) 1202(4)

C(35A)-C(34A)-C(39A) 1196(3)

C(35A)-C(34A)-P(2A) 1178(3)

C(39A)-C(34A)-P(2A) 1226(3)

C(34A)-C(35A)-C(36A) 1199(4)

C(37A)-C(36A)-C(35A) 1198(5)

C(38A)-C(37A)-C(36A) 1203(4)

C(37A)-C(38A)-C(39A) 1204(4)

C(38A)-C(39A)-C(34A) 1200(4)

C(41A)-C(40A)-C(45A) 1200

C(41A)-C(40A)-P(2A) 1219(4)

C(45A)-C(40A)-P(2A) 1181(4)

C(42A)-C(41A)-C(40A) 1200

C(41A)-C(42A)-C(43A) 1200

C(42A)-C(43A)-C(44A) 1200

C(45A)-C(44A)-C(43A) 1200

C(44A)-C(45A)-C(40A) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2A) 1242(5)

C(45)-C(40)-P(2A) 1152(6)

C(40)-C(41)-C(42) 1200

C(43)-C(42)-C(41) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

226

C(35A)-C(36A) 1394(6)

C(36A)-C(37A) 1377(7)

C(37A)-C(38A) 1369(7)

C(38A)-C(39A) 1374(5)

C(40A)-C(41A) 13900

C(40A)-C(45A) 13900

C(41A)-C(42A) 13900

C(42A)-C(43A) 13900

C(43A)-C(44A) 13900

C(44A)-C(45A) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46A)-C(51A) 1374(5)

C(46A)-C(47A) 1390(5)

C(47A)-C(48A) 1378(5)

C(48A)-C(49A) 1366(6)

C(49A)-C(50A) 1372(6)

C(50A)-C(51A) 1397(5)

Pd(1B)-P(2B) 22980(9)

Pd(1B)-P(1B) 23261(9)

Pd(1B)-S(1B) 23293(9)

Pd(1B)-S(3B) 23476(10)

P(1B)-C(28) 1800(6)

P(1B)-C(22B) 1817(3)

P(1B)-C(16B) 1822(3)

P(1B)-C(28B) 1853(3)

P(2B)-C(46B) 1725(3)

P(2B)-C(40) 1811(7)

P(2B)-C(34B) 1819(4)

P(2B)-C(40B) 1849(4)

P(2B)-C(46) 1911(5)

S(1B)-C(2B) 1719(4)

C(2B)-N(4B) 1312(5)

C(2B)-S(3B) 1722(4)

N(4B)-C(15B) 1434(7)

N(4B)-C(5) 1434(11)

N(4B)-C(5B) 1523(9)

N(4B)-C(15) 1553(9)

C(5B)-C(6B) 1527(11)

C(6B)-C(7B) 1513(9)

C(7B)-Si(8B) 1842(7)

Si(8B)-O(11B) 1612(6)

Si(8B)-O(9B) 1626(8)

Si(8B)-O(13B) 1629(5)

O(9B)-C(10B) 1426(12)

O(11B)-C(12B) 1431(10)

O(13B)-C(14B) 1383(10)

C(5)-C(6) 1496(12)

C(6)-C(7) 1488(10)

C(7)-Si(8) 1861(8)

Si(8)-O(9) 1577(9)

Si(8)-O(13) 1600(8)

Si(8)-O(11) 1640(8)

O(9)-C(10) 1372(13)

O(11)-C(12) 1411(10)

O(13)-C(14) 1388(12)

C(16B)-C(17B) 1369(5)

C(44)-C(45)-C(40) 1200

C(51A)-C(46A)-C(47A) 1192(3)

C(51A)-C(46A)-P(2A) 1215(3)

C(47A)-C(46A)-P(2A) 1194(3)

C(48A)-C(47A)-C(46A) 1205(4)

C(49A)-C(48A)-C(47A) 1200(4)

C(48A)-C(49A)-C(50A) 1203(4)

C(49A)-C(50A)-C(51A) 1200(4)

C(46A)-C(51A)-C(50A) 1200(4)

P(2B)-Pd(1B)-P(1B) 9991(3)

P(2B)-Pd(1B)-S(1B) 9282(3)

P(1B)-Pd(1B)-S(1B) 16611(3)

P(2B)-Pd(1B)-S(3B) 16751(4)

P(1B)-Pd(1B)-S(3B) 9257(3)

S(1B)-Pd(1B)-S(3B) 7472(4)

C(28)-P(1B)-C(22B) 1115(3)

C(28)-P(1B)-C(16B) 1024(4)

C(22B)-P(1B)-C(16B) 10549(16)

C(22B)-P(1B)-C(28B) 1015(2)

C(16B)-P(1B)-C(28B) 1044(2)

C(28)-P(1B)-Pd(1B) 1174(3)

C(22B)-P(1B)-Pd(1B) 10938(12)

C(16B)-P(1B)-Pd(1B) 10984(12)

C(28B)-P(1B)-Pd(1B) 1245(2)

C(46B)-P(2B)-C(34B) 1031(2)

C(40)-P(2B)-C(34B) 1057(4)

C(46B)-P(2B)-C(40B) 1035(3)

C(34B)-P(2B)-C(40B) 1050(2)

C(40)-P(2B)-C(46) 994(5)

C(34B)-P(2B)-C(46) 1146(3)

C(46B)-P(2B)-Pd(1B) 12210(18)

C(40)-P(2B)-Pd(1B) 1163(4)

C(34B)-P(2B)-Pd(1B) 11240(13)

C(40B)-P(2B)-Pd(1B) 1092(3)

C(46)-P(2B)-Pd(1B) 10795(19)

C(2B)-S(1B)-Pd(1B) 8727(14)

N(4B)-C(2B)-S(1B) 1242(3)

N(4B)-C(2B)-S(3B) 1247(3)

S(1B)-C(2B)-S(3B) 1111(2)

C(2B)-S(3B)-Pd(1B) 8661(13)

C(2B)-N(4B)-C(15B) 1252(5)

C(2B)-N(4B)-C(5) 1241(9)

C(2B)-N(4B)-C(5B) 1207(6)

C(15B)-N(4B)-C(5B) 1135(6)

C(2B)-N(4B)-C(15) 1156(5)

C(5)-N(4B)-C(15) 1200(9)

N(4B)-C(5B)-C(6B) 1098(7)

C(7B)-C(6B)-C(5B) 1152(7)

C(6B)-C(7B)-Si(8B) 1124(5)

O(11B)-Si(8B)-O(9B) 1112(4)

O(11B)-Si(8B)-O(13B) 1081(3)

O(9B)-Si(8B)-O(13B) 1049(4)

O(11B)-Si(8B)-C(7B) 1091(3)

O(9B)-Si(8B)-C(7B) 1110(4)

O(13B)-Si(8B)-C(7B) 1124(3)

C(10B)-O(9B)-Si(8B) 1228(7)

C(12B)-O(11B)-Si(8B) 1249(6)

C(14B)-O(13B)-Si(8B) 1273(7)

N(4B)-C(5)-C(6) 1110(10)

C(7)-C(6)-C(5) 1143(10)

C(6)-C(7)-Si(8) 1165(7)

227

C(16B)-C(21B) 1378(5)

C(17B)-C(18B) 1386(5)

C(18B)-C(19B) 1359(6)

C(19B)-C(20B) 1360(6)

C(20B)-C(21B) 1384(5)

C(22B)-C(23B) 1383(5)

C(22B)-C(27B) 1385(5)

C(23B)-C(24B) 1384(6)

C(24B)-C(25B) 1362(7)

C(25B)-C(26B) 1364(7)

C(26B)-C(27B) 1373(5)

C(28B)-C(29B) 13900

C(28B)-C(33B) 13900

C(29B)-C(30B) 13900

C(30B)-C(31B) 13900

C(31B)-C(32B) 13900

C(32B)-C(33B) 13900

C(28)-C(29) 13900

C(28)-C(33) 13900

C(29)-C(30) 13900

C(30)-C(31) 13900

C(31)-C(32) 13900

C(32)-C(33) 13900

C(34B)-C(35B) 1381(6)

C(34B)-C(39B) 1396(6)

C(35B)-C(36B) 1394(6)

C(36B)-C(37B) 1388(7)

C(37B)-C(38B) 1363(8)

C(38B)-C(39B) 1383(7)

C(40B)-C(41B) 13900

C(40B)-C(45B) 13900

C(41B)-C(42B) 13900

C(42B)-C(43B) 13900

C(43B)-C(44B) 13900

C(44B)-C(45B) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46B)-C(47B) 13900

C(46B)-C(51B) 13900

C(47B)-C(48B) 13900

C(48B)-C(49B) 13900

C(49B)-C(50B) 13900

C(50B)-C(51B) 13900

C(46)-C(47) 13900

C(46)-C(51) 13900

C(47)-C(48) 13900

C(48)-C(49) 13900

C(49)-C(50) 13900

C(50)-C(51) 13900

P(60)-F(65) 1563(4)

P(60)-F(62) 1570(4)

P(60)-F(64) 1572(4)

P(60)-F(63) 1581(4)

P(60)-F(66) 1592(4)

P(60)-F(61) 1601(4)

P(60)-F(62) 1557(11)

P(60)-F(64) 1562(11)

O(9)-Si(8)-O(13) 1091(6)

O(9)-Si(8)-O(11) 1115(5)

O(13)-Si(8)-O(11) 1066(4)

O(9)-Si(8)-C(7) 1042(6)

O(13)-Si(8)-C(7) 1119(4)

O(11)-Si(8)-C(7) 1135(4)

C(10)-O(9)-Si(8) 1269(9)

C(12)-O(11)-Si(8) 1245(7)

C(14)-O(13)-Si(8) 1277(8)

C(17B)-C(16B)-C(21B) 1181(3)

C(17B)-C(16B)-P(1B) 1190(3)

C(21B)-C(16B)-P(1B) 1229(3)

C(16B)-C(17B)-C(18B) 1213(4)

C(19B)-C(18B)-C(17B) 1199(4)

C(18B)-C(19B)-C(20B) 1197(4)

C(19B)-C(20B)-C(21B) 1206(4)

C(16B)-C(21B)-C(20B) 1204(4)

C(23B)-C(22B)-C(27B) 1181(3)

C(23B)-C(22B)-P(1B) 1225(3)

C(27B)-C(22B)-P(1B) 1194(3)

C(22B)-C(23B)-C(24B) 1204(4)

C(25B)-C(24B)-C(23B) 1204(4)

C(24B)-C(25B)-C(26B) 1198(4)

C(25B)-C(26B)-C(27B) 1203(4)

C(26B)-C(27B)-C(22B) 1209(4)

C(29B)-C(28B)-C(33B) 1200

C(29B)-C(28B)-P(1B) 1201(3)

C(33B)-C(28B)-P(1B) 1199(3)

C(28B)-C(29B)-C(30B) 1200

C(31B)-C(30B)-C(29B) 1200

C(30B)-C(31B)-C(32B) 1200

C(31B)-C(32B)-C(33B) 1200

C(32B)-C(33B)-C(28B) 1200

C(29)-C(28)-C(33) 1200

C(29)-C(28)-P(1B) 1209(5)

C(33)-C(28)-P(1B) 1190(5)

C(30)-C(29)-C(28) 1200

C(29)-C(30)-C(31) 1200

C(30)-C(31)-C(32) 1200

C(33)-C(32)-C(31) 1200

C(32)-C(33)-C(28) 1200

C(35B)-C(34B)-C(39B) 1196(4)

C(35B)-C(34B)-P(2B) 1173(3)

C(39B)-C(34B)-P(2B) 1230(4)

C(34B)-C(35B)-C(36B) 1205(4)

C(37B)-C(36B)-C(35B) 1192(5)

C(38B)-C(37B)-C(36B) 1202(5)

C(37B)-C(38B)-C(39B) 1213(5)

C(38B)-C(39B)-C(34B) 1191(5)

C(41B)-C(40B)-C(45B) 1200

C(41B)-C(40B)-P(2B) 1245(4)

C(45B)-C(40B)-P(2B) 1153(4)

C(40B)-C(41B)-C(42B) 1200

C(43B)-C(42B)-C(41B) 1200

C(44B)-C(43B)-C(42B) 1200

C(43B)-C(44B)-C(45B) 1200

C(44B)-C(45B)-C(40B) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2B) 1183(7)

C(45)-C(40)-P(2B) 1217(7)

C(42)-C(41)-C(40) 1200

228

P(60)-F(63) 1568(11)

P(60)-F(65) 1571(11)

P(60)-F(61) 1585(11)

P(60)-F(66) 1605(11)

P(70)-F(73) 1564(3)

P(70)-F(71) 1570(3)

P(70)-F(74) 1570(3)

P(70)-F(75) 1577(3)

P(70)-F(72) 1586(3)

P(70)-F(76) 1592(3)

C(80)-Cl(82) 1647(11)

C(80)-Cl(81) 1747(11)

C(90)-Cl(92) 165(5)

C(90)-Cl(91) 185(7)

P(2A)-Pd(1A)-P(1A) 10199(3)

P(2A)-Pd(1A)-S(1A) 9315(3)

P(1A)-Pd(1A)-S(1A) 16444(3)

P(2A)-Pd(1A)-S(3A) 16753(3)

P(1A)-Pd(1A)-S(3A) 8973(3)

S(1A)-Pd(1A)-S(3A) 7492(3)

C(22A)-P(1A)-C(28A) 1062(2)

C(22A)-P(1A)-C(16A) 1044(2)

C(28A)-P(1A)-C(16A) 10468(16)

C(28A)-P(1A)-C(22) 960(5)

C(16A)-P(1A)-C(22) 1101(5)

C(22A)-P(1A)-Pd(1A) 10918(18)

C(28A)-P(1A)-Pd(1A) 12376(11)

C(16A)-P(1A)-Pd(1A) 10703(12)

C(22)-P(1A)-Pd(1A) 1144(4)

C(46A)-P(2A)-C(34A) 10586(16)

C(46A)-P(2A)-C(40A) 989(3)

C(34A)-P(2A)-C(40A) 1086(3)

C(46A)-P(2A)-C(40) 1060(4)

C(34A)-P(2A)-C(40) 1032(4)

C(46A)-P(2A)-Pd(1A) 11826(12)

C(34A)-P(2A)-Pd(1A) 11366(12)

C(40A)-P(2A)-Pd(1A) 1103(3)

C(40)-P(2A)-Pd(1A) 1086(4)

C(2A)-S(1A)-Pd(1A) 8685(13)

N(4A)-C(2A)-S(3A) 1252(3)

N(4A)-C(2A)-S(1A) 1234(3)

S(3A)-C(2A)-S(1A) 1114(2)

C(2A)-S(3A)-Pd(1A) 8652(12)

C(2A)-N(4A)-C(5A) 1217(3)

C(2A)-N(4A)-C(15A) 1220(3)

C(5A)-N(4A)-C(15A) 1162(3)

N(4A)-C(5A)-C(6A) 1100(3)

C(7A)-C(6A)-C(5A) 1121(3)

C(6A)-C(7A)-Si(8A) 1149(3)

C(6A)-C(7A)-Si(8) 1142(3)

O(13A)-Si(8A)-O(9A) 1067(3)

O(13A)-Si(8A)-O(11A) 1115(3)

O(9A)-Si(8A)-O(11A) 1063(3)

O(13A)-Si(8A)-C(7A) 1115(3)

O(9A)-Si(8A)-C(7A) 1113(3)

O(11A)-Si(8A)-C(7A) 1093(3)

C(10A)-O(9A)-Si(8A) 1226(5)

C(12A)-O(11A)-Si(8A) 1220(5)

C(14A)-O(13A)-Si(8A) 1221(6)

O(9)-Si(8)-O(11) 1128(5)

C(41)-C(42)-C(43) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

C(44)-C(45)-C(40) 1200

C(47B)-C(46B)-C(51B) 1200

C(47B)-C(46B)-P(2B) 1224(3)

C(51B)-C(46B)-P(2B) 1176(3)

C(46B)-C(47B)-C(48B) 1200

C(47B)-C(48B)-C(49B) 1200

C(50B)-C(49B)-C(48B) 1200

C(49B)-C(50B)-C(51B) 1200

C(50B)-C(51B)-C(46B) 1200

C(47)-C(46)-C(51) 1200

C(47)-C(46)-P(2B) 1201(3)

C(51)-C(46)-P(2B) 1199(3)

C(48)-C(47)-C(46) 1200

C(49)-C(48)-C(47) 1200

C(50)-C(49)-C(48) 1200

C(49)-C(50)-C(51) 1200

C(50)-C(51)-C(46) 1200

F(65)-P(60)-F(62) 921(3)

F(65)-P(60)-F(64) 890(3)

F(62)-P(60)-F(64) 1789(4)

F(65)-P(60)-F(63) 1788(3)

F(62)-P(60)-F(63) 887(3)

F(64)-P(60)-F(63) 902(3)

F(65)-P(60)-F(66) 899(3)

F(62)-P(60)-F(66) 900(3)

F(64)-P(60)-F(66) 903(3)

F(63)-P(60)-F(66) 910(3)

F(65)-P(60)-F(61) 901(3)

F(62)-P(60)-F(61) 893(3)

F(64)-P(60)-F(61) 903(3)

F(63)-P(60)-F(61) 890(3)

F(66)-P(60)-F(61) 1793(4)

F(62)-P(60)-F(64) 1789(9)

F(62)-P(60)-F(63) 890(7)

F(64)-P(60)-F(63) 910(7)

F(62)-P(60)-F(65) 896(7)

F(64)-P(60)-F(65) 904(7)

F(63)-P(60)-F(65) 1783(9)

F(62)-P(60)-F(61) 904(7)

F(64)-P(60)-F(61) 907(7)

F(63)-P(60)-F(61) 901(7)

F(65)-P(60)-F(61) 909(7)

F(62)-P(60)-F(66) 901(7)

F(64)-P(60)-F(66) 888(7)

F(63)-P(60)-F(66) 893(7)

F(65)-P(60)-F(66) 897(7)

F(61)-P(60)-F(66) 1792(10)

F(73)-P(70)-F(71) 910(2)

F(73)-P(70)-F(74) 912(2)

F(71)-P(70)-F(74) 8971(19)

F(73)-P(70)-F(75) 1774(2)

F(71)-P(70)-F(75) 8995(18)

F(74)-P(70)-F(75) 913(2)

F(73)-P(70)-F(72) 898(2)

F(71)-P(70)-F(72) 9080(18)

F(74)-P(70)-F(72) 1789(2)

F(75)-P(70)-F(72) 8775(19)

F(73)-P(70)-F(76) 8966(18)

229

O(9)-Si(8)-O(13) 1017(5)

O(11)-Si(8)-O(13) 1130(5)

O(9)-Si(8)-C(7A) 1118(5)

O(11)-Si(8)-C(7A) 1074(4)

F(71)-P(70)-F(76) 1790(2)

F(74)-P(70)-F(76) 8954(17)

F(75)-P(70)-F(76) 8944(18)

F(72)-P(70)-F(76) 8994(17)

Cl(82)-C(80)-Cl(81) 1144(7)

Cl(92)-C(90)-Cl(91) 1077(16)











230

b = 147655(6) Aring = 76579(4)deg

c = 162359(7) Aring = 81131(3)deg




F(000) 1228

















Pd(1)-P(2) 22919(8)

Pd(1)-P(1) 23209(8)

Pd(1)-S(1) 23312(8)

Pd(1)-S(3) 23603(8)

P(1)-C(37) 1818(3)

P(1)-C(31) 1820(4)

P(1)-C(25) 1823(4)

P(2)-C(43) 1813(4)

P(2)-C(55) 1820(4)

P(2)-C(49) 1834(3)

S(1)-C(2) 1724(4)

C(2)-N(4) 1310(5)

C(2)-S(3) 1724(3)

N(4)-C(15) 1475(5)

N(4)-C(5) 1483(5)

C(5)-C(6) 1505(6)

C(6)-C(7) 1489(7)

C(7)-Si(8) 1873(5)

Si(8)-O(11) 1496(7)

Si(8)-O(13) 1557(11)

Si(8)-O(9) 1565(12)

Si(8)-O(9) 1624(6)

Si(8)-O(13) 1633(5)

S(3)-C(2)-S(1) 11213(19)

C(2)-S(3)-Pd(1) 8590(12)

C(2)-N(4)-C(15) 1217(3)

C(2)-N(4)-C(5) 1206(3)

C(15)-N(4)-C(5) 1177(3)

N(4)-C(5)-C(6) 1148(4)

C(7)-C(6)-C(5) 1142(4)

C(6)-C(7)-Si(8) 1144(3)

O(13)-Si(8)-O(9) 1104(10)

O(11)-Si(8)-O(9) 1059(5)

O(11)-Si(8)-O(13) 1110(3)

O(9)-Si(8)-O(13) 1031(4)

O(13)-Si(8)-O(11) 1029(7)

O(9)-Si(8)-O(11) 1063(8)

O(11)-Si(8)-C(7) 1136(3)

O(13)-Si(8)-C(7) 1206(7)

O(9)-Si(8)-C(7) 1088(12)

O(9)-Si(8)-C(7) 1139(6)

O(13)-Si(8)-C(7) 1089(3)

O(11)-Si(8)-C(7) 1069(7)

C(10)-O(9)-Si(8) 1278(8)

C(12)-O(11)-Si(8) 1307(7)

C(14)-O(13)-Si(8) 1264(7)

231

Si(8)-O(11) 1664(11)

O(9)-C(10) 1395(9)

O(11)-C(12) 1457(8)

O(13)-C(14) 1401(9)

O(9)-C(10) 1410(13)

O(11)-C(12) 1438(14)

O(13)-C(14) 1399(14)

C(15)-C(16) 1517(5)

C(16)-C(17) 1540(6)

C(17)-Si(18) 1853(5)

Si(18)-O(19) 1609(4)

Si(18)-O(21) 1614(4)

Si(18)-O(23) 1620(13)

Si(18)-O(23) 1636(5)

Si(18)-O(19) 1649(13)

Si(18)-O(21) 1658(14)

O(19)-C(20) 1413(8)

O(21)-C(22) 1370(9)

O(23)-C(24) 1359(9)

O(19)-C(20) 1398(16)

O(21)-C(22) 1396(17)

O(23)-C(24) 1392(16)

C(25)-C(26) 1393(5)

C(25)-C(30) 1399(5)

C(26)-C(27) 1388(6)

C(27)-C(28) 1372(7)

C(28)-C(29) 1376(7)

C(29)-C(30) 1395(6)

C(31)-C(32) 1388(5)

C(31)-C(36) 1397(5)

C(32)-C(33) 1389(5)

C(33)-C(34) 1383(6)

C(34)-C(35) 1391(5)

C(35)-C(36) 1383(5)

C(37)-C(38) 1395(5)

C(37)-C(42) 1397(5)

C(38)-C(39) 1382(5)

C(39)-C(40) 1393(6)

C(40)-C(41) 1380(6)

C(41)-C(42) 1383(5)

C(43)-C(44) 1387(5)

C(43)-C(48) 1399(5)

C(44)-C(45) 1393(5)

C(45)-C(46) 1383(6)

C(46)-C(47) 1383(6)

C(47)-C(48) 1389(5)

C(49)-C(50) 1384(5)

C(49)-C(54) 1404(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1377(7)

C(52)-C(53) 1384(7)

C(53)-C(54) 1394(5)

C(55)-C(60) 1391(5)

C(55)-C(56) 1394(5)

C(56)-C(57) 1384(6)

C(57)-C(58) 1386(7)

C(58)-C(59) 1382(7)

C(59)-C(60) 1392(6)

P(3)-F(6) 1588(3)

P(3)-F(5) 1590(3)

P(3)-F(3) 1591(3)

C(10)-O(9)-Si(8) 1321(16)

C(12)-O(11)-Si(8) 1203(13)

C(14)-O(13)-Si(8) 1323(16)

N(4)-C(15)-C(16) 1126(3)

C(15)-C(16)-C(17) 1103(3)

C(16)-C(17)-Si(18) 1159(3)

O(19)-Si(18)-O(21) 1125(4)

O(19)-Si(18)-O(23) 1106(3)

O(21)-Si(18)-O(23) 1077(3)

O(23)-Si(18)-O(19) 1101(10)

O(23)-Si(18)-O(21) 1067(11)

O(19)-Si(18)-O(21) 1059(10)

O(19)-Si(18)-C(17) 1084(2)

O(21)-Si(18)-C(17) 1107(4)

O(23)-Si(18)-C(17) 1215(11)

O(23)-Si(18)-C(17) 1068(3)

O(19)-Si(18)-C(17) 1003(9)

O(21)-Si(18)-C(17) 1112(16)

C(20)-O(19)-Si(18) 1270(6)

C(22)-O(21)-Si(18) 1283(6)

C(24)-O(23)-Si(18) 1306(7)

C(20)-O(19)-Si(18) 1250(17)

C(22)-O(21)-Si(18) 1231(18)

C(24)-O(23)-Si(18) 1266(19)

C(26)-C(25)-C(30) 1189(4)

C(26)-C(25)-P(1) 1195(3)

C(30)-C(25)-P(1) 1215(3)

C(27)-C(26)-C(25) 1204(4)

C(28)-C(27)-C(26) 1209(4)

C(27)-C(28)-C(29) 1191(4)

C(28)-C(29)-C(30) 1215(4)

C(29)-C(30)-C(25) 1192(4)

C(32)-C(31)-C(36) 1202(3)

C(32)-C(31)-P(1) 1202(3)

C(36)-C(31)-P(1) 1195(3)

C(31)-C(32)-C(33) 1193(3)

C(34)-C(33)-C(32) 1206(3)

C(33)-C(34)-C(35) 1201(3)

C(36)-C(35)-C(34) 1198(3)

C(35)-C(36)-C(31) 1201(3)

C(38)-C(37)-C(42) 1186(3)

C(38)-C(37)-P(1) 1181(3)

C(42)-C(37)-P(1) 1233(3)

C(39)-C(38)-C(37) 1207(3)

C(38)-C(39)-C(40) 1204(4)

C(41)-C(40)-C(39) 1189(4)

C(40)-C(41)-C(42) 1212(4)

C(41)-C(42)-C(37) 1201(4)

C(44)-C(43)-C(48) 1197(3)

C(44)-C(43)-P(2) 1250(3)

C(48)-C(43)-P(2) 1153(3)

C(43)-C(44)-C(45) 1194(4)

C(46)-C(45)-C(44) 1208(4)

C(45)-C(46)-C(47) 1200(4)

C(46)-C(47)-C(48) 1198(4)

C(47)-C(48)-C(43) 1203(4)

C(50)-C(49)-C(54) 1194(3)

C(50)-C(49)-P(2) 1226(3)

C(54)-C(49)-P(2) 1179(3)

C(49)-C(50)-C(51) 1203(4)

C(52)-C(51)-C(50) 1201(4)

232

P(3)-F(4) 1591(3)

P(3)-F(1) 1591(3)

P(3)-F(2) 1606(3)

P(2)-Pd(1)-P(1) 9913(3)

P(2)-Pd(1)-S(1) 9341(3)

P(1)-Pd(1)-S(1) 16715(3)

P(2)-Pd(1)-S(3) 16839(3)

P(1)-Pd(1)-S(3) 9221(3)

S(1)-Pd(1)-S(3) 7514(3)

C(37)-P(1)-C(31) 10350(15)

C(37)-P(1)-C(25) 10696(16)

C(31)-P(1)-C(25) 10397(16)

C(37)-P(1)-Pd(1) 12280(11)

C(31)-P(1)-Pd(1) 11250(11)

C(25)-P(1)-Pd(1) 10556(11)

C(43)-P(2)-C(55) 11078(16)

C(43)-P(2)-C(49) 10469(16)

C(55)-P(2)-C(49) 10265(16)

C(43)-P(2)-Pd(1) 10997(12)

C(55)-P(2)-Pd(1) 11546(12)

C(49)-P(2)-Pd(1) 11259(11)

C(2)-S(1)-Pd(1) 8681(12)

N(4)-C(2)-S(3) 1239(3)

N(4)-C(2)-S(1) 1239(3)

C(51)-C(52)-C(53) 1203(4)

C(52)-C(53)-C(54) 1200(4)

C(53)-C(54)-C(49) 1198(4)

C(60)-C(55)-C(56) 1195(3)

C(60)-C(55)-P(2) 1194(3)

C(56)-C(55)-P(2) 1210(3)

C(57)-C(56)-C(55) 1198(4)

C(56)-C(57)-C(58) 1207(4)

C(59)-C(58)-C(57) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(55)-C(60)-C(59) 1202(4)

F(6)-P(3)-F(5) 8938(18)

F(6)-P(3)-F(3) 9022(16)

F(5)-P(3)-F(3) 1796(2)

F(6)-P(3)-F(4) 9002(16)

F(5)-P(3)-F(4) 9024(18)

F(3)-P(3)-F(4) 8977(16)

F(6)-P(3)-F(1) 17916(19)

F(5)-P(3)-F(1) 913(2)

F(3)-P(3)-F(1) 8906(18)

F(4)-P(3)-F(1) 904(2)

F(6)-P(3)-F(2) 8873(16)

F(5)-P(3)-F(2) 9101(19)

F(3)-P(3)-F(2) 8896(16)

F(4)-P(3)-F(2) 1782(2)

F(1)-P(3)-F(2) 908(2)

233



example)

v

Acknowledgements













they are missing








vi












vii

Abstract




























viii










ix

Abbreviations






x

Contents

Declaration ii


Publication iv

Acknowledgement v

Abstract vii

Abbreviations ix

Contents x



1





6












xi

16 References 31






45


51







25 Conclusion 66

26 References 67





73


73



79



xii



84


87




90


35 Conclusion 96

36 References 98





102





112



118




121

45 Conclusion 128

46 References 130

xiii





133




136


(37) 138









148


149


152

55 Conclusion 154

56 References 156


61 Conclusions 158

62 Future work 159

xiv





731 KS2CN(CH2py)2 (1) 163

732 [Au(S2CN(CH2py)2)(PPh3)] (2) 163

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3) 164





738 [Ni(S2C-N(CH2py)2)] (8) 166







170


170


7317 (SC6H4CO2H-4)2 (17) 172

7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18) 172



173


174

xv






741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 178

742 [Pd(S2CNEt2)2] (24) 178



(26) 179

745 [Pd(Me2dazdt)2]I6 (27) 180

746 [PdI2(Me2dazdt)] (28) 180

747 [Pd(Cy2DTO)2]I8 (29) 180



751 (TBA)2[Pd2I6] (30) 186

752 Trans-PdI2(PPh3)2 (31) 186

753 [PdI2(dppe)] (32) 187

754 [PdI2(dppf)] (33) 187







xvi




195


195


196


8 Appendices



201



204



(22)

208



212



216


219



223



223


229



1

























2











(Figure 112)8




3




















4
























5













6














7




















8























9












catalysis









10






























carbon (C-C) bond

11















C)42


12





















metals


13









mechanisms















14



















15

















16














(80)56











17


















18


















19



























20


























21




















22














23












of product92







24
















25






















0

500

1000

1500

2000

2500

1992 1997 2003 2008 2014

Pri

ce (

USD

pe

r O

z)

Year

Pt

Pd

26





















27



























PGMs112






28



concerns114


















143

29


15 Thesis overview










also investigated



30











31

16 References
























32

37 2466ndash2468

























33























70 Chem Abs 1969 71 114951




34
























35























36


37

























(Figure 211)


38
















manner













39
















mz 200











40




at mz 274


41


































42


































43














44

































45




ligand










Figure 231












46













47






















formulation










48

















complexes
















49















50
































51





nitrogen)

























52


















53





























54




















55


































56




















8764(18)deg]37


57































58


















59
















(Figure 245)








60










NP1 (Figure 246)








61




















0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

(

)

Temperature ()

62


















63







0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

64



















65



0

10

20

30

40

50

60

70

80

90

100

0 100 200 300 400 500 600 700 800

Wei

ght

()

Temperature ()

66

25 Conclusion















67

26 References





















68























69









70































71

























72

















catalystsrdquo19












73































74
















75






















76









77











Pt(PPh3)2

27

2354(1) 2355(1)

1318 (6)

1723(5) 1725(5)

1118(3)

7467 (4)

Pd(dppf)27

23370(1) 2358(1)

1322(6)

1725(5) 1735(5)

1121(3)

7518(5)

Pd(PPh3)2 (25-A)

23304(10) 23536(10)

1302(5)

1722(4) 1735(4)

1112(2)

7504(4)

Pd(PPh3)2 (25-B)

23388 (8) 23479(9)

1326(4)

1714(4) 1727(4)

11276(19)

7536(3)





(Figure 324)

78












Pd(dppf)26

23348(6) 23516(6) 23347(6) 23445(7)

1313(3) 1323(3)

1728(2) 1719(2) 1709(2) 1723(2)

11188(14) 11215(13)

7507(2) 7498(2)

Pd(PPh3)2 (26)

23720(16) 23190(15) 23735(17) 23180(15

1323(8) 1316(9)

1715(7) 1718(6) 1722(7) 1727(7)

1132(4) 1119(4)

7528(5) 7505(5)

79























80
















81















A

Me MeOH 12 22 95

Et EtOH 51 24 80



B Me MeOH 19 18 80

82



reaction























block and vials





83



























byproducts

84








impact


(SOCDTC)







86

75

8784

87

69

8784

0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Perc

enta

ge y

ield

(

)


22hr 2hr

85


time


















30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Pd loading (mol)

86



















0

10

20

30

40

50

60

70

80

90

100

23 24 25 26

Yie

ld

)

Catalyst


87































88










(h)

Yield

()

SD

A

Et

23 2 89 (20)

24 2 83 (10)

25 2 64 (21)

26 2 65 (35)

Pri

23 8 90 (14)

24 24 99 (00)

25 4 97 (12)

26 8 91 (25)

CH2CF3

23 4 92 (10)

24 4 99 (00)

25 2 99 (06)

26 2 95 (17)

B

Me

23 2 66 (02)

24 6 40 (02)

25 2 78 (02)

26 2 46 (44)






89





























90



(mol)

Temperature

(degC)

Time

(h)

Yield

()

A

Me

Me

27 1 100

100

2 87

Pd(OAc)2 1 22 95

Me 27 1 50 2 67

Me Pd(OAc)2 1 50 2 33


catalysts (SOCDTO)










0

20

40

60

80

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

1 mol 2 mol

91


















0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5

Yie

ld (

)

Time (hours)

1 mol 2 mol

92



(mol)

Time

(h)

Yield

()

SD

()

1

1 39 05

A

Pri

27

2 48 06

3 52 07

4 52 09

5 53 08

Pri

27

2

1 74 31

2 79 23

3 81 27

4 83 27

5 83 30

A

CF3CH2

27

2

1 49 05

2 72 09

3 85 11

4 92 00

5 96 05






or 2 hours

93


T = 50 degC








89

9899 99

85

92

9596

75

80

85

90

95

100

105

1 2 3 4

Yie

ld (

)

Time (hours)


40

50

60

70

80

90

100

0 1 2 3 4 5

Yiel

d (

)

Time (hours)

EtOH iPrOH

94













0

10

20

30

40

50

60

70

80

90

100

0 1 2 3 4 5 6 7 8 9 10

Yie

ld (

)

Time (hours)


95







(mol)

Time

(h)

Yield

()

SD

()

2

1 53 11

B

OMe

28

2 95 05

3 100 05

4 100 00

5 100 00

B

OMe

29

2

1 54 20

2 89 08

3 99 02

4 100 00

5 100 00











96




method (100)

35 Conclusion



























97









98

36 References




















99











100






























101













and Singulair56

















102






















secondary source







103
















104























105













above11













sections






106

























107









A

1 mol

Me 2 94 ( 02)

Et 2 43 ( 02)

Pri 2 52 ( 47)

CH2CF3 2 93 ( 30)

2 mol

Me 2 99 ( 04)

EtOH 2 81 ( 33)

Pri 2 75 ( 40)

CH2CF3 2 99 ( 15)













108






















original work

109













50

MeOH

11 Pd

1 34

2 39

5 73

22 87

100

MeOH

11 Pd

1 91

2 90

5 92

22 92







A MeOH 11 22 95

110




















111








nm17

















112






catalyst
















113








0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25

Yiel

d (

)

Time (hours)


114

















0

20

40

60

80

100

120

0 5 10 15 20 25 30

Yiel

d (

)

Time (hours)


115













B Me 1 mol 2 80 (02)

2 mol 2 87 (16)







116





















B

MeOH

1 mol

2 96 ( 02)

4 94 ( 17)

6 96 ( 03)

24 95 (12)

B

MeOH

2 mol

2 99 (06)

4 99 (04)

6 99 (04)

24 99 (05)



117







C AcOH 1 mol 2 61 ( 30)

2 mol 2 83 ( 40)













C

AcOH

1 mol

2 44 ( 28)

4 55 ( 06)

6 62 ( 25)

24 71 ( 16)

C

AcOH

2 mol

2 71 ( 78)

4 71 ( 21)

6 72 ( 13)

24 85 ( 38)

118


















119




























120









coupling reaction



















reading

121













coupling reactions












122


Catalyst Pd

loadings

(mol )

Yield ()


[PdI2(PPh3)2] (31)

05



























123

















coupling reactions




80

85

90

95

100

105


Yiel

d (

)

Catalysts

30 min 60 min

124















K2CO3 in ethanol











125




















80

85

90

95

100

30 60 90

Yie

ld (

)

Time (min)

(TBA)₂[Pd₂I₆] (30) [PdCl₂(PPh₃)₂]

126

















0

10

20

30

40

50

60

70

80

90

100

90 120 150

Pro

du

ct y

ield

(

)

Time (min)


127




60 968 plusmn 04


60 973 plusmn 15


60 996 plusmn 01


60 995 plusmn 01









0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


128










45 Conclusion











0

10

20

30

40

50

60

70

80

90

100

60 90 120

Pro

du

ct y

ield

(

)

Time (min)


129




excellent yield










130

46 References























131
























132
































133














oxidant PhI(OAc)2











134






















135
















products










both complexes







136
















137












138



25-A

23304(10)

23536(10)

1302(5)

1722(4)

1735(4)

1112(2)

7504(4)

36-A

23294(9)

23458(9)

1306(4)

1726(3)

1717(4)

1114(2)

7492(3)

36-B

23293(9)

23476(10)

1312(5)

1719(4)

1722(4)

1111(2)

7472(3)








C(10)-O(9)-Si(8) 1226˚ (5) 1228˚ (7) 02˚

C(12)-O(11)-Si(8) 1220˚ (5) 1249˚ (6) 29˚

C(14)-O(13)-Si(8) 1221˚ (6) 1273˚ (7) 52˚







139











140













Reaction

Catalyst Pd

(mol)

Temperature

(degC)

Time

(h)

Yield

()

SD

A

36

1

100

2

85 ( 06)

37 85 ( 07)

23 87 (10)

141











product








0

10

20

30

40

50

60

70

1 2 3 4 5 6

Yiel

d (

)

Time (hours)

36 37

142



















0

20

40

60

80

100

120

0 1 2 3 4 5 6

Yiel

d (

)


36 37

143









(h)

Yield

()

SD

Et

23 2 89 (20)

A

36 24 99 (04)

37 24 42 (34)

CH2CF3

23 4 92 (10)

36 6 98 (02)

37 6 90 (17)

B Me 23 2 66 (02)

37 6 60 (38)















144





magnetic field14















145






















146



nanoparticles















147



















ethanol and dried









148







and dried















149








complexes













physisorbed

150











nanoparticles


151






















60

65

70

75

80

85

90

95

100

0 100 200 300 400 500 600

Weig

ht (

)

Temperature ()


152



palladium catalyst










h)








153



36SiO2Fe3O4 32 13 5 -

36SiO2Fe3O4 32 27 10 6



























154









55 Conclusion






















155






156

56 References























157










158


61 Conclusions



















donor groups










159

















system

62 Future work













160



161

7 Experimental





























162


























163


731 KS2CN(CH2py)2 (1)








mg (84) IR 2923 (νC-H) 2361 1591 1570 1474 1434 (νC-N) 1358 1302 1183





(100) [M-K]ˉ

732 [Au(S2CN(CH2py)2)(PPh3)] (2)












N 56

164

733 [Pt(S2CN(CH2py)2)(PPh3)](PF6) (3)














37 Found C 497 H 37 N 35















C 585 H 44 N 34

165




















677 H 48 N 41











166









45 N 35











1915 (νCO) 1589 1570 1475 1432 1409 1207 1157 1090 1001 750 689 cmndash1





37 Found C 699 H 47 N 37

738 [Ni(S2C-N(CH2py)2)] (8)




167









H 40 N 138 Found C 433 H 36 N 108




















199616) C 641 H 45 N 14 Found C 637 H 42 N 18

168



















H 43 N 16













169







H 42 N 10












715 H 51 N 10











170











(CO) 1890 (CO) 1531 (OCO) 1481 1433 1391 1184 1090 979 827 743 692 cmndash












= 208951) C 615 H 41 N 13 Found C 614 H 39 N 14








171








226170) C 643 H 39 N 12 Found C 641 H 38 N 12



















C 509 H 33 N 13

172

7317 (SC6H4CO2H-4)2 (17)






2669 2552 1676 (VCO) 1591 1423 1323 1292 1181 1116 933 850 cmndash1 1H NMR



7318 [Ru(dppm)2(O2CC6H4S-4)2](PF6)2 (18)





















H 42 Found C 586 H 42

173































174









= 138224) C 617 H 42 Found C 617 H 41


















175






1535 1481 1434 1419 1176 1095 862 744 692 cm-1 1H NMR (CD2Cl2) 578 (d







H 33 N 16 Found C 526 H 34 N 17



















176














x 2 2 x 2H PCH2P) 661 (m 4H C6H5) 710 726 738 754 772 794 (m x 6 36H


















177





178


741 [Pd(S2CNEt2)(PPh3)2]PF6 (23) 925













742 [Pd(S2CNEt2)2] (24)26













179






(79) IR (ATR) 1514 1480 1434 1280 1239 1094 999 (νC-S) 831 (νPF) cm-1 1H






524 H 38 N 16 Found C 525 H 37 N 16




















180


745 [Pd(Me2dazdt)2]I6 (27)







1429 1393 1357 1330 1287 1283 1107 1073 1028 981 825 743610 581 532


NCH2 JHH = 67 Hz)









1527 1460 1423 1395 1359 1330 1286 1264 1223 1114 1073 1027 958 897



literature28

747 [Pd(Cy2DTO)2]I8 (29)





181







199 H 29 N 33 Found C 203 H 28 N 34
















data

182





183

























184












method data (99)





Hz 20 Hz) 726 (dd 1H J = 80 Hz 10 Hz) 419 (s3H)





3H J = 70 Hz)




60 Hz) 150 (t 6H J = 60 Hz)



185






3H)

186


751 (TBA)2[Pd2I6]30 (30)


























187

753 [PdI2(dppe)] (32)





Yield 325 mg (87) IR 3052 1437 1100 998 877 811 701 688 678 cm-1 1H




754 [PdI2(dppf)] (33)






= 242 (s dppf) ppm







188












step












189






















190






by 1H NMR




746 (dd 1H JHH = 786 Hz 42 Hz) 586 (s2H) 216 (s 3H)











isolated yield

191



















192



















C 310 H 60 N 45












193






H 66 N 31 Found C 341 H 67 N 32



















47 N 14






194





























195






(129 g)














603 563 (νFeO) cm-1









196

SiO236 NP



SiO236 NP











36SiO2Fe3O4


588 (νFeO) cm-1


37SiO2Fe3O4



197










catalyst system





NMR



198

References




















199






















200

2013 49 11358ndash60

201

Appendices



N(CH2py)2)(CO)(PPh3)2] (5)









b = 148523(7) Aring = 82606(3)deg

c = 179728(7) Aring = 87478(3)deg




202

F(000) 1164

















Ru(1)-C(28) 1836(3)

Ru(1)-C(19) 2083(3)

Ru(1)-P(2) 23706(8)

Ru(1)-P(1) 23823(8)

Ru(1)-S(3) 24740(8)

Ru(1)-S(1) 25025(8)

P(1)-C(29) 1834(3)

P(1)-C(35) 1834(3)

P(1)-C(41) 1845(4)

P(2)-C(53) 1827(3)

P(2)-C(59) 1837(3)

P(2)-C(47) 1845(3)

S(1)-C(2) 1715(3)

C(2)-N(4) 1333(4)

C(2)-S(3) 1698(3)

N(4)-C(5) 1457(5)

N(4)-C(12) 1461(4)

C(5)-C(6) 1516(5)

C(6)-N(7) 1344(5)

C(6)-C(11) 1372(5)

N(7)-C(8) 1353(6)

C(8)-C(9) 1382(7)

C(9)-C(10) 1366(7)

C(10)-C(11) 1368(6)

C(12)-C(13) 1519(6)

C(13)-N(14) 1335(5)

C(13)-C(18) 1370(6)

N(14)-C(15) 1360(7)

C(15)-C(16) 1339(9)

C(16)-C(17) 1354(8)

C(17)-C(18) 1398(7)

C(29)-P(1)-Ru(1) 11804(10)

C(35)-P(1)-Ru(1) 11715(11)

C(41)-P(1)-Ru(1) 11341(12)

C(53)-P(2)-C(59) 10292(15)

C(53)-P(2)-C(47) 10443(14)

C(59)-P(2)-C(47) 9991(14)

C(53)-P(2)-Ru(1) 11295(10)

C(59)-P(2)-Ru(1) 11877(11)

C(47)-P(2)-Ru(1) 11586(11)

C(2)-S(1)-Ru(1) 8783(12)

N(4)-C(2)-S(3) 1241(3)

N(4)-C(2)-S(1) 1227(3)

S(3)-C(2)-S(1) 11319(18)

C(2)-S(3)-Ru(1) 8915(11)

C(2)-N(4)-C(5) 1221(3)

C(2)-N(4)-C(12) 1210(3)

C(5)-N(4)-C(12) 1168(3)

N(4)-C(5)-C(6) 1153(3)

N(7)-C(6)-C(11) 1231(4)

N(7)-C(6)-C(5) 1139(3)

C(11)-C(6)-C(5) 1230(3)

C(6)-N(7)-C(8) 1168(4)

N(7)-C(8)-C(9) 1230(4)

C(10)-C(9)-C(8) 1182(4)

C(9)-C(10)-C(11) 1201(4)

C(10)-C(11)-C(6) 1187(4)

N(4)-C(12)-C(13) 1144(3)

N(14)-C(13)-C(18) 1227(4)

N(14)-C(13)-C(12) 1133(4)

C(18)-C(13)-C(12) 1240(3)

C(13)-N(14)-C(15) 1159(5)

203

C(19)-C(20) 1333(5)

C(20)-C(21) 1477(5)

C(21)-C(22) 1395(5)

C(21)-C(26) 1403(5)

C(22)-C(23) 1388(5)

C(23)-C(24) 1386(6)

C(24)-C(25) 1384(6)

C(24)-C(27) 1519(6)

C(25)-C(26) 1386(5)

C(28)-O(28) 1138(4)

C(29)-C(34) 1388(5)

C(29)-C(30) 1397(5)

C(30)-C(31) 1383(5)

C(31)-C(32) 1387(6)

C(32)-C(33) 1378(6)

C(33)-C(34) 1396(5)

C(35)-C(36) 1373(6)

C(35)-C(40) 1393(5)

C(36)-C(37) 1382(5)

C(37)-C(38) 1380(6)

C(38)-C(39) 1359(7)

C(39)-C(40) 1404(5)

C(41)-C(42) 1383(6)

C(41)-C(46) 1393(5)

C(42)-C(43) 1389(7)

C(43)-C(44) 1372(9)

C(44)-C(45) 1371(8)

C(45)-C(46) 1392(6)

C(47)-C(52) 1386(4)

C(47)-C(48) 1393(5)

C(48)-C(49) 1384(5)

C(49)-C(50) 1384(5)

C(50)-C(51) 1381(6)

C(51)-C(52) 1396(5)

C(53)-C(58) 1388(5)

C(53)-C(54) 1393(5)

C(54)-C(55) 1407(5)

C(55)-C(56) 1375(6)

C(56)-C(57) 1384(6)

C(57)-C(58) 1393(5)

C(59)-C(64) 1384(5)

C(59)-C(60) 1395(5)

C(60)-C(61) 1394(5)

C(61)-C(62) 1381(7)

C(62)-C(63) 1378(7)

C(63)-C(64) 1399(5)

C(28)-Ru(1)-C(19) 9900(14)

C(28)-Ru(1)-P(2) 9001(10)

C(19)-Ru(1)-P(2) 8442(9)

C(28)-Ru(1)-P(1) 8661(11)

C(19)-Ru(1)-P(1) 8546(9)

P(2)-Ru(1)-P(1) 16869(3)

C(28)-Ru(1)-S(3) 16962(11)

C(19)-Ru(1)-S(3) 9137(9)

P(2)-Ru(1)-S(3) 9142(3)

P(1)-Ru(1)-S(3) 9385(3)

C(28)-Ru(1)-S(1) 9981(11)

C(19)-Ru(1)-S(1) 16110(9)

P(2)-Ru(1)-S(1) 9381(3)

P(1)-Ru(1)-S(1) 9739(3)

C(16)-C(15)-N(14) 1249(5)

C(15)-C(16)-C(17) 1188(5)

C(16)-C(17)-C(18) 1187(5)

C(13)-C(18)-C(17) 1190(4)

C(20)-C(19)-Ru(1) 1263(2)

C(19)-C(20)-C(21) 1261(3)

C(22)-C(21)-C(26) 1174(3)

C(22)-C(21)-C(20) 1231(3)

C(26)-C(21)-C(20) 1195(3)

C(23)-C(22)-C(21) 1211(3)

C(24)-C(23)-C(22) 1212(4)

C(25)-C(24)-C(23) 1181(4)

C(25)-C(24)-C(27) 1218(4)

C(23)-C(24)-C(27) 1202(4)

C(24)-C(25)-C(26) 1213(3)

C(25)-C(26)-C(21) 1210(3)

O(28)-C(28)-Ru(1) 1776(3)

C(34)-C(29)-C(30) 1192(3)

C(34)-C(29)-P(1) 1224(3)

C(30)-C(29)-P(1) 1183(3)

C(31)-C(30)-C(29) 1202(3)

C(30)-C(31)-C(32) 1204(3)

C(33)-C(32)-C(31) 1196(3)

C(32)-C(33)-C(34) 1204(4)

C(29)-C(34)-C(33) 1201(3)

C(36)-C(35)-C(40) 1179(3)

C(36)-C(35)-P(1) 1208(3)

C(40)-C(35)-P(1) 1214(3)

C(35)-C(36)-C(37) 1214(4)

C(38)-C(37)-C(36) 1208(5)

C(39)-C(38)-C(37) 1187(4)

C(38)-C(39)-C(40) 1210(4)

C(35)-C(40)-C(39) 1202(4)

C(42)-C(41)-C(46) 1184(4)

C(42)-C(41)-P(1) 1223(3)

C(46)-C(41)-P(1) 1193(3)

C(41)-C(42)-C(43) 1208(5)

C(44)-C(43)-C(42) 1201(5)

C(45)-C(44)-C(43) 1201(4)

C(44)-C(45)-C(46) 1201(4)

C(45)-C(46)-C(41) 1205(4)

C(52)-C(47)-C(48) 1186(3)

C(52)-C(47)-P(2) 1223(3)

C(48)-C(47)-P(2) 1189(2)

C(49)-C(48)-C(47) 1207(3)

C(50)-C(49)-C(48) 1203(4)

C(51)-C(50)-C(49) 1196(3)

C(50)-C(51)-C(52) 1200(3)

C(47)-C(52)-C(51) 1207(3)

C(58)-C(53)-C(54) 1197(3)

C(58)-C(53)-P(2) 1197(2)

C(54)-C(53)-P(2) 1199(3)

C(53)-C(54)-C(55) 1196(3)

C(56)-C(55)-C(54) 1201(3)

C(55)-C(56)-C(57) 1204(3)

C(56)-C(57)-C(58) 1200(4)

C(53)-C(58)-C(57) 1203(3)

C(64)-C(59)-C(60) 1194(3)

C(64)-C(59)-P(2) 1210(3)

C(60)-C(59)-P(2) 1196(3)

C(61)-C(60)-C(59) 1201(4)

204

S(3)-Ru(1)-S(1) 6983(3)

C(29)-P(1)-C(35) 10221(15)

C(29)-P(1)-C(41) 10252(17)

C(35)-P(1)-C(41) 10111(16)

C(62)-C(61)-C(60) 1199(4)

C(63)-C(62)-C(61) 1205(4)

C(62)-C(63)-C(64) 1198(4)

C(59)-C(64)-C(63) 1204(4)





5(C H2 Cl2)






b = 217537(9) Aring = 92572(4)deg

c = 304002(14) Aring = 90deg

205




F(000) 3136

















Ru(1)-O(3) 2161(4)

Ru(1)-O(1) 2232(4)

Ru(1)-P(43) 22640(16)

Ru(1)-P(13) 22916(17)

Ru(1)-P(11) 23361(16)

Ru(1)-P(41) 23570(16)

Ru(1)-C(2) 2531(6)

O(1)-C(2) 1267(7)

C(2)-O(3) 1260(7)

C(2)-C(4) 1489(8)

C(4)-C(9) 1370(9)

C(4)-C(5) 1380(8)

C(5)-C(6) 1387(8)

C(6)-N(7) 1333(8)

C(6)-C(6)1 1475(12)

N(7)-C(8) 1338(9)

C(8)-C(9) 1390(9)

P(11)-C(20) 1806(6)

P(11)-C(14) 1818(6)

P(11)-C(12) 1829(6)

C(12)-P(13) 1854(6)

P(13)-C(26) 1815(6)

P(13)-C(32) 1820(6)

C(14)-C(15) 1371(9)

C(14)-C(19) 1395(8)

C(15)-C(16) 1395(9)

C(16)-C(17) 1373(10)

C(5)-C(6)-C(6)1 1212(7)

C(6)-N(7)-C(8) 1175(6)

N(7)-C(8)-C(9) 1236(6)

C(4)-C(9)-C(8) 1180(6)

C(20)-P(11)-C(14) 1050(3)

C(20)-P(11)-C(12) 1088(3)

C(14)-P(11)-C(12) 1074(3)

C(20)-P(11)-Ru(1) 1157(2)

C(14)-P(11)-Ru(1) 1235(2)

C(12)-P(11)-Ru(1) 950(2)

P(11)-C(12)-P(13) 948(3)

C(26)-P(13)-C(32) 1043(3)

C(26)-P(13)-C(12) 1024(3)

C(32)-P(13)-C(12) 1072(3)

C(26)-P(13)-Ru(1) 1188(2)

C(32)-P(13)-Ru(1) 1249(2)

C(12)-P(13)-Ru(1) 958(2)

C(15)-C(14)-C(19) 1200(6)

C(15)-C(14)-P(11) 1205(5)

C(19)-C(14)-P(11) 1194(5)

C(14)-C(15)-C(16) 1200(6)

C(17)-C(16)-C(15) 1194(7)

C(18)-C(17)-C(16) 1208(7)

C(17)-C(18)-C(19) 1202(7)

C(18)-C(19)-C(14) 1195(7)

C(25)-C(20)-C(21) 1195(6)

C(25)-C(20)-P(11) 1227(5)

206

C(17)-C(18) 1370(11)

C(18)-C(19) 1377(9)

C(20)-C(25) 1371(9)

C(20)-C(21) 1395(9)

C(21)-C(22) 1370(10)

C(22)-C(23) 1375(12)

C(23)-C(24) 1383(13)

C(24)-C(25) 1397(11)

C(26)-C(31) 1375(9)

C(26)-C(27) 1402(8)

C(27)-C(28) 1383(9)

C(28)-C(29) 1361(10)

C(29)-C(30) 1388(10)

C(30)-C(31) 1384(10)

C(32)-C(37) 1378(9)

C(32)-C(33) 1412(9)

C(33)-C(34) 1376(10)

C(34)-C(35) 1354(11)

C(35)-C(36) 1381(11)

C(36)-C(37) 1385(9)

P(41)-C(50) 1818(6)

P(41)-C(44) 1823(7)

P(41)-C(42) 1851(6)

C(42)-P(43) 1849(6)

P(43)-C(62) 1811(6)

P(43)-C(56) 1829(7)

C(44)-C(49) 1384(9)

C(44)-C(45) 1387(9)

C(45)-C(46) 1383(10)

C(46)-C(47) 1377(12)

C(47)-C(48) 1386(12)

C(48)-C(49) 1366(11)

C(50)-C(55) 1375(9)

C(50)-C(51) 1398(9)

C(51)-C(52) 1386(9)

C(52)-C(53) 1364(11)

C(53)-C(54) 1385(11)

C(54)-C(55) 1382(10)

C(56)-C(57) 1357(9)

C(56)-C(61) 1388(9)

C(57)-C(58) 1392(10)

C(58)-C(59) 1376(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1380(10)

C(62)-C(63) 1386(9)

C(62)-C(67) 1395(8)

C(63)-C(64) 1396(9)

C(64)-C(65) 1362(10)

C(65)-C(66) 1370(10)

C(66)-C(67) 1385(8)

B(70)-C(83) 1628(11)

B(70)-C(77) 1635(11)

B(70)-C(89) 1644(11)

B(70)-C(71) 1659(10)

C(71)-C(76) 1367(10)

C(71)-C(72) 1398(10)

C(72)-C(73) 1367(11)

C(73)-C(74) 1346(13)

C(74)-C(75) 1370(13)

C(75)-C(76) 1403(11)

C(77)-C(82) 1376(10)

C(21)-C(20)-P(11) 1172(5)

C(22)-C(21)-C(20) 1209(7)

C(21)-C(22)-C(23) 1193(8)

C(22)-C(23)-C(24) 1211(8)

C(23)-C(24)-C(25) 1191(8)

C(20)-C(25)-C(24) 1201(7)

C(31)-C(26)-C(27) 1182(6)

C(31)-C(26)-P(13) 1203(5)

C(27)-C(26)-P(13) 1207(5)

C(28)-C(27)-C(26) 1201(6)

C(29)-C(28)-C(27) 1208(6)

C(28)-C(29)-C(30) 1201(7)

C(31)-C(30)-C(29) 1192(7)

C(26)-C(31)-C(30) 1217(7)

C(37)-C(32)-C(33) 1184(6)

C(37)-C(32)-P(13) 1193(5)

C(33)-C(32)-P(13) 1221(5)

C(34)-C(33)-C(32) 1195(7)

C(35)-C(34)-C(33) 1215(7)

C(34)-C(35)-C(36) 1199(7)

C(35)-C(36)-C(37) 1199(8)

C(32)-C(37)-C(36) 1208(7)

C(50)-P(41)-C(44) 1009(3)

C(50)-P(41)-C(42) 1075(3)

C(44)-P(41)-C(42) 1055(3)

C(50)-P(41)-Ru(1) 1224(2)

C(44)-P(41)-Ru(1) 1243(2)

C(42)-P(41)-Ru(1) 9385(19)

P(43)-C(42)-P(41) 952(3)

C(62)-P(43)-C(56) 1029(3)

C(62)-P(43)-C(42) 1067(3)

C(56)-P(43)-C(42) 1063(3)

C(62)-P(43)-Ru(1) 1294(2)

C(56)-P(43)-Ru(1) 1125(2)

C(42)-P(43)-Ru(1) 970(2)

C(49)-C(44)-C(45) 1201(7)

C(49)-C(44)-P(41) 1214(5)

C(45)-C(44)-P(41) 1185(5)

C(46)-C(45)-C(44) 1188(7)

C(47)-C(46)-C(45) 1211(8)

C(46)-C(47)-C(48) 1195(8)

C(49)-C(48)-C(47) 1200(8)

C(48)-C(49)-C(44) 1206(7)

C(55)-C(50)-C(51) 1187(6)

C(55)-C(50)-P(41) 1226(5)

C(51)-C(50)-P(41) 1185(5)

C(52)-C(51)-C(50) 1195(6)

C(53)-C(52)-C(51) 1208(7)

C(52)-C(53)-C(54) 1203(7)

C(55)-C(54)-C(53) 1188(7)

C(50)-C(55)-C(54) 1218(7)

C(57)-C(56)-C(61) 1194(6)

C(57)-C(56)-P(43) 1190(5)

C(61)-C(56)-P(43) 1214(5)

C(56)-C(57)-C(58) 1204(7)

C(59)-C(58)-C(57) 1206(7)

C(60)-C(59)-C(58) 1184(7)

C(59)-C(60)-C(61) 1214(7)

C(60)-C(61)-C(56) 1197(7)

C(63)-C(62)-C(67) 1188(6)

C(63)-C(62)-P(43) 1211(5)

207

C(77)-C(78) 1406(11)

C(78)-C(79) 1390(11)

C(79)-C(80) 1367(12)

C(80)-C(81) 1350(13)

C(81)-C(82) 1412(12)

C(83)-C(88) 1388(11)

C(83)-C(84) 1410(11)

C(84)-C(85) 1398(12)

C(85)-C(86) 1379(14)

C(86)-C(87) 1372(14)

C(87)-C(88) 1399(12)

C(89)-C(94) 1392(10)

C(89)-C(90) 1412(10)

C(90)-C(91) 1387(11)

C(91)-C(92) 1365(13)

C(92)-C(93) 1353(12)

C(93)-C(94) 1402(11)

C(100)-Cl(2) 1707(11)

C(100)-Cl(1) 1727(11)

C(110)-Cl(4) 1639(14)

C(110)-Cl(3) 1720(12)

C(120)-Cl(5) 1670(15)

C(120)-Cl(6) 1751(16)

O(3)-Ru(1)-O(1) 5979(15)

O(3)-Ru(1)-P(43) 9947(12)

O(1)-Ru(1)-P(43) 15664(11)

O(3)-Ru(1)-P(13) 16018(12)

O(1)-Ru(1)-P(13) 10841(11)

P(43)-Ru(1)-P(13) 9445(6)

O(3)-Ru(1)-P(11) 9159(12)

O(1)-Ru(1)-P(11) 9023(11)

P(43)-Ru(1)-P(11) 10176(6)

P(13)-Ru(1)-P(11) 7170(6)

O(3)-Ru(1)-P(41) 9644(12)

O(1)-Ru(1)-P(41) 9776(11)

P(43)-Ru(1)-P(41) 7245(6)

P(13)-Ru(1)-P(41) 10118(6)

P(11)-Ru(1)-P(41) 17076(6)

O(3)-Ru(1)-C(2) 2985(16)

O(1)-Ru(1)-C(2) 3003(16)

P(43)-Ru(1)-C(2) 12894(14)

P(13)-Ru(1)-C(2) 13584(14)

P(11)-Ru(1)-C(2) 8942(13)

P(41)-Ru(1)-C(2) 9982(13)

C(2)-O(1)-Ru(1) 882(3)

O(3)-C(2)-O(1) 1201(5)

O(3)-C(2)-C(4) 1191(5)

O(1)-C(2)-C(4) 1208(5)

O(3)-C(2)-Ru(1) 586(3)

O(1)-C(2)-Ru(1) 618(3)

C(4)-C(2)-Ru(1) 1735(4)

C(2)-O(3)-Ru(1) 916(4)

C(67)-C(62)-P(43) 1201(5)

C(62)-C(63)-C(64) 1199(6)

C(65)-C(64)-C(63) 1203(7)

C(64)-C(65)-C(66) 1207(6)

C(65)-C(66)-C(67) 1197(6)

C(66)-C(67)-C(62) 1206(6)

C(83)-B(70)-C(77) 1137(6)

C(83)-B(70)-C(89) 1124(6)

C(77)-B(70)-C(89) 1039(6)

C(83)-B(70)-C(71) 1032(6)

C(77)-B(70)-C(71) 1114(6)

C(89)-B(70)-C(71) 1124(6)

C(76)-C(71)-C(72) 1146(7)

C(76)-C(71)-B(70) 1245(7)

C(72)-C(71)-B(70) 1209(7)

C(73)-C(72)-C(71) 1239(8)

C(74)-C(73)-C(72) 1201(9)

C(73)-C(74)-C(75) 1188(8)

C(74)-C(75)-C(76) 1206(9)

C(71)-C(76)-C(75) 1219(8)

C(82)-C(77)-C(78) 1150(7)

C(82)-C(77)-B(70) 1238(7)

C(78)-C(77)-B(70) 1208(7)

C(79)-C(78)-C(77) 1230(8)

C(80)-C(79)-C(78) 1199(9)

C(81)-C(80)-C(79) 1191(9)

C(80)-C(81)-C(82) 1211(8)

C(77)-C(82)-C(81) 1220(8)

C(88)-C(83)-C(84) 1154(8)

C(88)-C(83)-B(70) 1249(8)

C(84)-C(83)-B(70) 1196(8)

C(85)-C(84)-C(83) 1222(10)

C(86)-C(85)-C(84) 1197(10)

C(87)-C(86)-C(85) 1201(10)

C(86)-C(87)-C(88) 1194(11)

C(83)-C(88)-C(87) 1232(10)

C(94)-C(89)-C(90) 1145(7)

C(94)-C(89)-B(70) 1249(6)

C(90)-C(89)-B(70) 1204(7)

C(91)-C(90)-C(89) 1227(8)

C(92)-C(91)-C(90) 1202(8)

C(93)-C(92)-C(91) 1196(9)

C(92)-C(93)-C(94) 1206(8)

C(89)-C(94)-C(93) 1224(8)

Cl(2)-C(100)-Cl(1) 1150(7)

Cl(4)-C(110)-Cl(3) 1199(8)

Cl(5)-C(120)-Cl(6) 1119(9)

208





25(C H2 Cl2)






b = 147789(5) Aring = 73377(3)deg

c = 214417(6) Aring = 75105(3)deg




F(000) 1926







209











Au(1)-P(11) 22545(16)

Au(1)-S(10) 23027(16)

Re(1)-C(83) 1895(7)

Re(1)-C(84) 1915(7)

Re(1)-C(85) 1931(9)

Re(1)-C(85) 1947(7)

Re(1)-N(43) 2161(5)

Re(1)-N(32) 2175(5)

Re(1)-Cl(1) 2271(8)

Re(1)-Cl(1) 2337(4)

Ru(1)-C(82) 1807(6)

Ru(1)-C(30) 2013(5)

Ru(1)-O(1) 2194(3)

Ru(1)-O(3) 2236(4)

Ru(1)-P(63) 23781(16)

Ru(1)-P(44) 23806(17)

Ru(1)-C(2) 2564(5)

C(85)-O(85) 1187(8)

C(85)-O(85) 1178(9)

O(1)-C(2) 1255(7)

C(2)-O(3) 1268(7)

C(2)-C(4) 1480(7)

C(4)-C(9) 1377(8)

C(4)-C(5) 1399(8)

C(5)-C(6) 1360(8)

C(6)-C(7) 1376(8)

C(7)-C(8) 1376(8)

C(7)-S(10) 1761(6)

C(8)-C(9) 1392(8)

P(11)-C(18) 1800(6)

P(11)-C(24) 1811(6)

P(11)-C(12) 1824(6)

C(12)-C(13) 1386(8)

C(12)-C(17) 1388(9)

C(13)-C(14) 1360(10)

C(14)-C(15) 1383(11)

C(15)-C(16) 1395(10)

C(16)-C(17) 1366(9)

C(18)-C(23) 1374(9)

C(18)-C(19) 1405(9)

C(19)-C(20) 1388(9)

C(20)-C(21) 1378(10)

C(21)-C(22) 1346(11)

C(30)-Ru(1)-C(2) 1308(2)

O(1)-Ru(1)-C(2) 2928(16)

O(3)-Ru(1)-C(2) 2965(16)

P(63)-Ru(1)-C(2) 8971(14)

P(44)-Ru(1)-C(2) 8897(14)

O(85)-C(85)-Re(1) 1747(13)

O(85)-C(85)-Re(1) 176(4)

C(2)-O(1)-Ru(1) 919(3)

O(1)-C(2)-O(3) 1194(5)

O(1)-C(2)-C(4) 1223(5)

O(3)-C(2)-C(4) 1183(5)

O(1)-C(2)-Ru(1) 588(3)

O(3)-C(2)-Ru(1) 607(3)

C(4)-C(2)-Ru(1) 1784(4)

C(2)-O(3)-Ru(1) 897(3)

C(9)-C(4)-C(5) 1186(5)

C(9)-C(4)-C(2) 1207(5)

C(5)-C(4)-C(2) 1207(6)

C(6)-C(5)-C(4) 1199(6)

C(5)-C(6)-C(7) 1226(6)

C(8)-C(7)-C(6) 1176(5)

C(8)-C(7)-S(10) 1237(5)

C(6)-C(7)-S(10) 1187(5)

C(7)-C(8)-C(9) 1212(6)

C(4)-C(9)-C(8) 1202(6)

C(7)-S(10)-Au(1) 1059(2)

C(18)-P(11)-C(24) 1048(3)

C(18)-P(11)-C(12) 1061(3)

C(24)-P(11)-C(12) 1055(3)

C(18)-P(11)-Au(1) 1112(2)

C(24)-P(11)-Au(1) 1164(2)

C(12)-P(11)-Au(1) 1120(2)

C(13)-C(12)-C(17) 1192(6)

C(13)-C(12)-P(11) 1191(5)

C(17)-C(12)-P(11) 1217(5)

C(14)-C(13)-C(12) 1206(7)

C(13)-C(14)-C(15) 1207(7)

C(14)-C(15)-C(16) 1188(6)

C(17)-C(16)-C(15) 1204(7)

C(16)-C(17)-C(12) 1203(7)

C(23)-C(18)-C(19) 1183(6)

C(23)-C(18)-P(11) 1231(5)

C(19)-C(18)-P(11) 1186(5)

210

C(22)-C(23) 1422(10)

C(24)-C(25) 1378(9)

C(24)-C(29) 1384(8)

C(25)-C(26) 1368(9)

C(26)-C(27) 1380(10)

C(27)-C(28) 1370(10)

C(28)-C(29) 1387(9)

C(30)-C(31) 1331(7)

C(31)-C(34) 1456(8)

N(32)-C(33) 1326(7)

N(32)-C(37) 1356(7)

C(33)-C(34) 1390(8)

C(34)-C(35) 1399(8)

C(35)-C(36) 1363(8)

C(36)-C(37) 1384(8)

C(37)-C(38) 1482(8)

C(38)-N(43) 1341(7)

C(38)-C(39) 1372(8)

C(39)-C(40) 1386(9)

C(40)-C(41) 1364(9)

C(41)-C(42) 1371(9)

C(42)-N(43) 1347(8)

P(44)-C(45) 1819(7)

P(44)-C(57) 1820(7)

P(44)-C(51) 1830(4)

P(44)-C(51) 1861(15)

C(45)-C(46) 1379(10)

C(45)-C(50) 1385(10)

C(46)-C(47) 1356(10)

C(47)-C(48) 1331(14)

C(48)-C(49) 1359(13)

C(49)-C(50) 1397(11)

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(51)-C(52) 13900

C(51)-C(56) 13900

C(52)-C(53) 13900

C(53)-C(54) 13900

C(54)-C(55) 13900

C(55)-C(56) 13900

C(57)-C(58) 1390(9)

C(57)-C(62) 1396(9)

C(58)-C(59) 1396(11)

C(59)-C(60) 1367(11)

C(60)-C(61) 1366(10)

C(61)-C(62) 1401(9)

P(63)-C(70) 1812(7)

P(63)-C(76) 1817(9)

P(63)-C(76) 1831(5)

P(63)-C(64) 1831(6)

C(64)-C(65) 1367(9)

C(64)-C(69) 1379(8)

C(65)-C(66) 1381(9)

C(66)-C(67) 1352(9)

C(67)-C(68) 1382(10)

C(68)-C(69) 1394(8)

C(70)-C(75) 1371(10)

C(20)-C(19)-C(18) 1209(6)

C(21)-C(20)-C(19) 1208(7)

C(22)-C(21)-C(20) 1184(7)

C(21)-C(22)-C(23) 1227(7)

C(18)-C(23)-C(22) 1189(7)

C(25)-C(24)-C(29) 1188(6)

C(25)-C(24)-P(11) 1219(5)

C(29)-C(24)-P(11) 1190(5)

C(26)-C(25)-C(24) 1212(6)

C(25)-C(26)-C(27) 1195(7)

C(28)-C(27)-C(26) 1206(7)

C(27)-C(28)-C(29) 1194(7)

C(24)-C(29)-C(28) 1205(7)

C(31)-C(30)-Ru(1) 1354(5)

C(30)-C(31)-C(34) 1249(6)

C(33)-N(32)-C(37) 1176(5)

C(33)-N(32)-Re(1) 1254(4)

C(37)-N(32)-Re(1) 1168(4)

N(32)-C(33)-C(34) 1257(6)

C(33)-C(34)-C(35) 1148(5)

C(33)-C(34)-C(31) 1212(5)

C(35)-C(34)-C(31) 1239(5)

C(36)-C(35)-C(34) 1211(6)

C(35)-C(36)-C(37) 1194(6)

N(32)-C(37)-C(36) 1213(5)

N(32)-C(37)-C(38) 1151(5)

C(36)-C(37)-C(38) 1235(5)

N(43)-C(38)-C(39) 1214(6)

N(43)-C(38)-C(37) 1151(5)

C(39)-C(38)-C(37) 1234(6)

C(38)-C(39)-C(40) 1208(6)

C(41)-C(40)-C(39) 1172(6)

C(40)-C(41)-C(42) 1201(6)

N(43)-C(42)-C(41) 1226(6)

C(38)-N(43)-C(42) 1179(5)

C(38)-N(43)-Re(1) 1180(4)

C(42)-N(43)-Re(1) 1241(4)

C(45)-P(44)-C(57) 1029(3)

C(45)-P(44)-C(51) 1036(4)

C(57)-P(44)-C(51) 1002(4)

C(45)-P(44)-C(51) 1043(12)

C(57)-P(44)-C(51) 1099(10)

C(45)-P(44)-Ru(1) 1140(2)

C(57)-P(44)-Ru(1) 1181(2)

C(51)-P(44)-Ru(1) 1160(3)

C(51)-P(44)-Ru(1) 1068(12)

C(46)-C(45)-C(50) 1180(7)

C(46)-C(45)-P(44) 1194(6)

C(50)-C(45)-P(44) 1226(6)

C(47)-C(46)-C(45) 1219(8)

C(48)-C(47)-C(46) 1204(9)

C(47)-C(48)-C(49) 1203(8)

C(48)-C(49)-C(50) 1208(9)

C(45)-C(50)-C(49) 1186(8)

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1173(4)

C(56)-C(51)-P(44) 1227(4)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

211

C(70)-C(71) 1386(9)

C(71)-C(72) 1392(12)

C(72)-C(73) 1341(13)

C(73)-C(74) 1368(13)

C(74)-C(75) 1396(11)

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(76)-C(77) 13900

C(76)-C(81) 13900

C(77)-C(78) 13900

C(78)-C(79) 13900

C(79)-C(80) 13900

C(80)-C(81) 13900

C(82)-O(82) 1152(7)

C(83)-O(83) 1152(7)

C(84)-O(84) 1138(8)

P(11)-Au(1)-S(10) 17634(6)

C(83)-Re(1)-C(84) 865(3)

C(83)-Re(1)-C(85) 861(15)

C(84)-Re(1)-C(85) 924(15)

C(83)-Re(1)-C(85) 896(5)

C(84)-Re(1)-C(85) 887(5)

C(83)-Re(1)-N(43) 1003(2)

C(84)-Re(1)-N(43) 1732(2)

C(85)-Re(1)-N(43) 884(14)

C(85)-Re(1)-N(43) 910(5)

C(83)-Re(1)-N(32) 1743(2)

C(84)-Re(1)-N(32) 986(2)

C(85)-Re(1)-N(32) 913(15)

C(85)-Re(1)-N(32) 930(5)

N(43)-Re(1)-N(32) 7463(18)

C(83)-Re(1)-Cl(1) 974(3)

C(84)-Re(1)-Cl(1) 941(3)

C(85)-Re(1)-Cl(1) 1729(14)

N(43)-Re(1)-Cl(1) 848(2)

N(32)-Re(1)-Cl(1) 847(2)

C(83)-Re(1)-Cl(1) 873(3)

C(84)-Re(1)-Cl(1) 926(3)

C(85)-Re(1)-Cl(1) 1766(5)

N(43)-Re(1)-Cl(1) 8805(17)

N(32)-Re(1)-Cl(1) 8998(17)

C(82)-Ru(1)-C(30) 917(3)

C(82)-Ru(1)-O(1) 1667(2)

C(30)-Ru(1)-O(1) 10156(19)

C(82)-Ru(1)-O(3) 1078(2)

C(30)-Ru(1)-O(3) 1604(2)

O(1)-Ru(1)-O(3) 5893(14)

C(82)-Ru(1)-P(63) 8796(19)

C(30)-Ru(1)-P(63) 9106(17)

O(1)-Ru(1)-P(63) 9197(11)

O(3)-Ru(1)-P(63) 8801(11)

C(82)-Ru(1)-P(44) 9536(19)

C(30)-Ru(1)-P(44) 8717(17)

O(1)-Ru(1)-P(44) 8519(11)

O(3)-Ru(1)-P(44) 9255(11)

P(63)-Ru(1)-P(44) 17628(6)

C(55)-C(56)-C(51) 1200

C(52)-C(51)-C(56) 1200

C(52)-C(51)-P(44) 1203(18)

C(56)-C(51)-P(44) 1196(18)

C(53)-C(52)-C(51) 1200

C(52)-C(53)-C(54) 1200

C(55)-C(54)-C(53) 1200

C(56)-C(55)-C(54) 1200

C(55)-C(56)-C(51) 1200

C(58)-C(57)-C(62) 1183(6)

C(58)-C(57)-P(44) 1217(6)

C(62)-C(57)-P(44) 1199(5)

C(57)-C(58)-C(59) 1199(8)

C(60)-C(59)-C(58) 1211(8)

C(61)-C(60)-C(59) 1200(7)

C(60)-C(61)-C(62) 1198(7)

C(57)-C(62)-C(61) 1208(7)

C(70)-P(63)-C(76) 1091(6)

C(70)-P(63)-C(76) 1009(4)

C(70)-P(63)-C(64) 1038(3)

C(76)-P(63)-C(64) 1055(7)

C(76)-P(63)-C(64) 1038(5)

C(70)-P(63)-Ru(1) 1150(2)

C(76)-P(63)-Ru(1) 1081(6)

C(76)-P(63)-Ru(1) 1166(4)

C(64)-P(63)-Ru(1) 11489(19)

C(65)-C(64)-C(69) 1180(6)

C(65)-C(64)-P(63) 1231(4)

C(69)-C(64)-P(63) 1189(5)

C(64)-C(65)-C(66) 1216(6)

C(67)-C(66)-C(65) 1204(7)

C(66)-C(67)-C(68) 1196(6)

C(67)-C(68)-C(69) 1195(6)

C(64)-C(69)-C(68) 1208(7)

C(75)-C(70)-C(71) 1178(7)

C(75)-C(70)-P(63) 1200(5)

C(71)-C(70)-P(63) 1221(6)

C(70)-C(71)-C(72) 1205(8)

C(73)-C(72)-C(71) 1195(8)

C(72)-C(73)-C(74) 1225(9)

C(73)-C(74)-C(75) 1173(10)

C(70)-C(75)-C(74) 1223(8)

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1210(6)

C(81)-C(76)-P(63) 1190(6)

C(76)-C(77)-C(78) 1200

C(79)-C(78)-C(77) 1200

C(78)-C(79)-C(80) 1200

C(81)-C(80)-C(79) 1200

C(80)-C(81)-C(76) 1200

C(77)-C(76)-C(81) 1200

C(77)-C(76)-P(63) 1215(10)

C(81)-C(76)-P(63) 1184(10)

C(78)-C(77)-C(76) 1200

C(77)-C(78)-C(79) 1200

C(80)-C(79)-C(78) 1200

C(79)-C(80)-C(81) 1200

C(80)-C(81)-C(76) 1200

O(82)-C(82)-Ru(1) 1771(5)

O(83)-C(83)-Re(1) 1771(7)

O(84)-C(84)-Re(1) 1793(6)

212

C(82)-Ru(1)-C(2) 1374(2)










b = 155218(4) Aring = 107289(3)deg

c = 268129(9) Aring = 90deg




F(000) 3784






213












Pd(1)-P(2) 22948(10)

Pd(1)-P(1) 23232(10)

Pd(1)-S(3) 23304(10)

Pd(1)-S(1) 23536(10)

Pd(2)-P(4) 22985(10)

Pd(2)-S(12) 23240(10)

Pd(2)-P(3) 23292(10)

Pd(2)-S(10) 23512(10)

P(1)-C(13) 1814(4)

P(1)-C(25) 1815(4)

P(1)-C(19) 1818(4)

P(2)-C(31) 1809(4)

P(2)-C(43) 1810(4)

P(2)-C(37) 1823(4)

P(3)-C(49) 1805(4)

P(3)-C(61) 1822(4)

P(3)-C(55) 1822(4)

P(4)-C(79) 1818(4)

P(4)-C(67) 1821(4)

P(4)-C(73) 1826(4)

S(1)-C(2) 1735(4)

C(2)-N(4) 1302(5)

C(2)-S(3) 1722(4)

N(4)-C(5) 1458(5)

N(4)-C(9) 1478(5)

C(5)-C(6) 1524(6)

C(6)-N(7) 1473(5)

N(7)-C(11) 1308(5)

N(7)-C(8) 1464(5)

C(8)-C(9) 1511(6)

S(10)-C(11) 1728(4)

C(11)-S(12) 1717(4)

C(13)-C(18) 1380(6)

C(13)-C(14) 1383(6)

C(14)-C(15) 1384(7)

C(15)-C(16) 1371(8)

C(16)-C(17) 1341(8)

C(17)-C(18) 1383(7)

C(19)-C(24) 1371(6)

C(19)-C(20) 1392(6)

C(20)-C(21) 1372(7)

C(79)-P(4)-C(73) 9763(18)

C(67)-P(4)-C(73) 1063(2)

C(79)-P(4)-Pd(2) 11555(13)

C(67)-P(4)-Pd(2) 10862(13)

C(73)-P(4)-Pd(2) 11746(14)

C(2)-S(1)-Pd(1) 8607(13)

N(4)-C(2)-S(3) 1232(3)

N(4)-C(2)-S(1) 1256(3)

S(3)-C(2)-S(1) 1112(2)

C(2)-S(3)-Pd(1) 8709(14)

C(2)-N(4)-C(5) 1228(3)

C(2)-N(4)-C(9) 1227(3)

C(5)-N(4)-C(9) 1145(3)

N(4)-C(5)-C(6) 1090(3)

N(7)-C(6)-C(5) 1095(3)

C(11)-N(7)-C(8) 1244(3)

C(11)-N(7)-C(6) 1220(3)

C(8)-N(7)-C(6) 1133(3)

N(7)-C(8)-C(9) 1103(3)

N(4)-C(9)-C(8) 1100(3)

C(11)-S(10)-Pd(2) 8619(13)

N(7)-C(11)-S(12) 1234(3)

N(7)-C(11)-S(10) 1253(3)

S(12)-C(11)-S(10) 1112(2)

C(11)-S(12)-Pd(2) 8729(13)

C(18)-C(13)-C(14) 1183(4)

C(18)-C(13)-P(1) 1234(3)

C(14)-C(13)-P(1) 1183(3)

C(13)-C(14)-C(15) 1211(5)

C(16)-C(15)-C(14) 1195(5)

C(17)-C(16)-C(15) 1194(5)

C(16)-C(17)-C(18) 1223(5)

C(13)-C(18)-C(17) 1192(5)

C(24)-C(19)-C(20) 1199(4)

C(24)-C(19)-P(1) 1194(3)

C(20)-C(19)-P(1) 1207(4)

C(21)-C(20)-C(19) 1199(5)

C(22)-C(21)-C(20) 1206(6)

C(21)-C(22)-C(23) 1211(5)

C(22)-C(23)-C(24) 1187(6)

214

C(21)-C(22) 1342(9)

C(22)-C(23) 1390(9)

C(23)-C(24) 1402(7)

C(25)-C(30) 1390(5)

C(25)-C(26) 1405(5)

C(26)-C(27) 1377(6)

C(27)-C(28) 1380(6)

C(28)-C(29) 1375(6)

C(29)-C(30) 1380(6)

C(31)-C(32) 1390(6)

C(31)-C(36) 1392(6)

C(32)-C(33) 1387(6)

C(33)-C(34) 1380(8)

C(34)-C(35) 1365(8)

C(35)-C(36) 1384(7)

C(37)-C(42) 1379(6)

C(37)-C(38) 1388(6)

C(38)-C(39) 1382(6)

C(39)-C(40) 1367(7)

C(40)-C(41) 1356(7)

C(41)-C(42) 1386(6)

C(43)-C(44) 1381(6)

C(43)-C(48) 1393(6)

C(44)-C(45) 1394(7)

C(45)-C(46) 1373(8)

C(46)-C(47) 1365(8)

C(47)-C(48) 1390(6)

C(49)-C(50) 1388(5)

C(49)-C(54) 1402(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1360(6)

C(52)-C(53) 1384(6)

C(53)-C(54) 1372(6)

C(55)-C(56) 1390(5)

C(55)-C(60) 1393(5)

C(56)-C(57) 1385(6)

C(57)-C(58) 1374(6)

C(58)-C(59) 1375(6)

C(59)-C(60) 1377(6)

C(61)-C(66) 1393(6)

C(61)-C(62) 1394(6)

C(62)-C(63) 1388(6)

C(63)-C(64) 1379(7)

C(64)-C(65) 1373(7)

C(65)-C(66) 1384(6)

C(67)-C(72) 1387(6)

C(67)-C(68) 1387(6)

C(68)-C(69) 1378(6)

C(69)-C(70) 1362(7)

C(70)-C(71) 1375(8)

C(71)-C(72) 1376(7)

C(73)-C(78) 1371(6)

C(73)-C(74) 1392(6)

C(74)-C(75) 1371(7)

C(75)-C(76) 1369(8)

C(76)-C(77) 1376(8)

C(77)-C(78) 1410(6)

C(79)-C(84) 1384(5)

C(79)-C(80) 1394(5)

C(80)-C(81) 1374(6)

C(81)-C(82) 1387(6)

C(19)-C(24)-C(23) 1198(5)

C(30)-C(25)-C(26) 1184(4)

C(30)-C(25)-P(1) 1208(3)

C(26)-C(25)-P(1) 1207(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1200(4)

C(29)-C(28)-C(27) 1201(4)

C(28)-C(29)-C(30) 1205(4)

C(29)-C(30)-C(25) 1204(4)

C(32)-C(31)-C(36) 1193(4)

C(32)-C(31)-P(2) 1192(3)

C(36)-C(31)-P(2) 1214(4)

C(33)-C(32)-C(31) 1204(5)

C(34)-C(33)-C(32) 1195(5)

C(35)-C(34)-C(33) 1205(5)

C(34)-C(35)-C(36) 1207(5)

C(35)-C(36)-C(31) 1196(5)

C(42)-C(37)-C(38) 1188(4)

C(42)-C(37)-P(2) 1230(3)

C(38)-C(37)-P(2) 1180(3)

C(39)-C(38)-C(37) 1200(4)

C(40)-C(39)-C(38) 1204(5)

C(41)-C(40)-C(39) 1201(4)

C(40)-C(41)-C(42) 1204(5)

C(37)-C(42)-C(41) 1203(4)

C(44)-C(43)-C(48) 1202(4)

C(44)-C(43)-P(2) 1243(4)

C(48)-C(43)-P(2) 1154(3)

C(43)-C(44)-C(45) 1192(5)

C(46)-C(45)-C(44) 1201(5)

C(47)-C(46)-C(45) 1211(5)

C(46)-C(47)-C(48) 1196(5)

C(47)-C(48)-C(43) 1198(5)

C(50)-C(49)-C(54) 1191(4)

C(50)-C(49)-P(3) 1196(3)

C(54)-C(49)-P(3) 1212(3)

C(49)-C(50)-C(51) 1197(4)

C(52)-C(51)-C(50) 1202(4)

C(51)-C(52)-C(53) 1209(4)

C(54)-C(53)-C(52) 1197(4)

C(53)-C(54)-C(49) 1204(4)

C(56)-C(55)-C(60) 1185(4)

C(56)-C(55)-P(3) 1219(3)

C(60)-C(55)-P(3) 1193(3)

C(57)-C(56)-C(55) 1200(4)

C(58)-C(57)-C(56) 1208(4)

C(57)-C(58)-C(59) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(59)-C(60)-C(55) 1209(4)

C(66)-C(61)-C(62) 1187(4)

C(66)-C(61)-P(3) 1201(3)

C(62)-C(61)-P(3) 1211(3)

C(63)-C(62)-C(61) 1199(4)

C(64)-C(63)-C(62) 1208(5)

C(65)-C(64)-C(63) 1194(4)

C(64)-C(65)-C(66) 1207(5)

C(65)-C(66)-C(61) 1204(4)

C(72)-C(67)-C(68) 1191(4)

C(72)-C(67)-P(4) 1188(3)

C(68)-C(67)-P(4) 1215(3)

C(69)-C(68)-C(67) 1199(5)

215

C(82)-C(83) 1375(6)

C(83)-C(84) 1368(5)

P(10)-F(13) 1549(4)

P(10)-F(15) 1560(4)

P(10)-F(14) 1560(3)

P(10)-F(12) 1564(4)

P(10)-F(11) 1582(3)

P(10)-F(16) 1592(3)

P(20)-F(23) 1557(3)

P(20)-F(21) 1565(3)

P(20)-F(26) 1573(3)

P(20)-F(24) 1582(3)

P(20)-F(22) 1584(3)

P(20)-F(25) 1589(3)

O(90)-C(91) 1361(6)

O(90)-C(93) 1397(7)

C(91)-C(92) 1483(8)

C(93)-C(94) 1393(8)

O(90)-C(91) 1341(10)

O(90)-C(93) 1345(10)

C(91)-C(92) 1452(10)

C(93)-C(94) 1451(10)

P(2)-Pd(1)-P(1) 10098(4)

P(2)-Pd(1)-S(3) 16943(4)

P(1)-Pd(1)-S(3) 8822(4)

P(2)-Pd(1)-S(1) 9507(4)

P(1)-Pd(1)-S(1) 16140(4)

S(3)-Pd(1)-S(1) 7504(4)

P(4)-Pd(2)-S(12) 17025(4)

P(4)-Pd(2)-P(3) 10004(4)

S(12)-Pd(2)-P(3) 8970(3)

P(4)-Pd(2)-S(10) 9535(3)

S(12)-Pd(2)-S(10) 7490(3)

P(3)-Pd(2)-S(10) 16452(4)

C(13)-P(1)-C(25) 10983(18)

C(13)-P(1)-C(19) 1033(2)

C(25)-P(1)-C(19) 10175(19)

C(13)-P(1)-Pd(1) 10736(14)

C(25)-P(1)-Pd(1) 10878(12)

C(19)-P(1)-Pd(1) 12519(13)

C(31)-P(2)-C(43) 10980(19)

C(31)-P(2)-C(37) 10173(17)

C(43)-P(2)-C(37) 10461(19)

C(31)-P(2)-Pd(1) 11826(15)

C(43)-P(2)-Pd(1) 10682(14)

C(37)-P(2)-Pd(1) 11481(13)

C(49)-P(3)-C(61) 10500(18)

C(49)-P(3)-C(55) 10370(18)

C(61)-P(3)-C(55) 10515(18)

C(49)-P(3)-Pd(2) 11419(12)

C(61)-P(3)-Pd(2) 11999(13)

C(55)-P(3)-Pd(2) 10732(12)

C(79)-P(4)-C(67) 11063(18)

C(70)-C(69)-C(68) 1209(5)

C(69)-C(70)-C(71) 1194(5)

C(70)-C(71)-C(72) 1209(5)

C(71)-C(72)-C(67) 1197(5)

C(78)-C(73)-C(74) 1201(4)

C(78)-C(73)-P(4) 1194(3)

C(74)-C(73)-P(4) 1189(3)

C(75)-C(74)-C(73) 1205(5)

C(76)-C(75)-C(74) 1197(5)

C(75)-C(76)-C(77) 1209(5)

C(76)-C(77)-C(78) 1196(5)

C(73)-C(78)-C(77) 1191(5)

C(84)-C(79)-C(80) 1198(4)

C(84)-C(79)-P(4) 1151(3)

C(80)-C(79)-P(4) 1246(3)

C(81)-C(80)-C(79) 1192(4)

C(80)-C(81)-C(82) 1206(4)

C(83)-C(82)-C(81) 1199(4)

C(84)-C(83)-C(82) 1201(4)

C(83)-C(84)-C(79) 1205(4)

F(13)-P(10)-F(15) 1779(3)

F(13)-P(10)-F(14) 913(3)

F(15)-P(10)-F(14) 902(3)

F(13)-P(10)-F(12) 903(3)

F(15)-P(10)-F(12) 882(3)

F(14)-P(10)-F(12) 1775(3)

F(13)-P(10)-F(11) 914(2)

F(15)-P(10)-F(11) 901(2)

F(14)-P(10)-F(11) 915(2)

F(12)-P(10)-F(11) 903(2)

F(13)-P(10)-F(16) 891(2)

F(15)-P(10)-F(16) 8948(19)

F(14)-P(10)-F(16) 8896(18)

F(12)-P(10)-F(16) 892(2)

F(11)-P(10)-F(16) 1793(2)

F(23)-P(20)-F(21) 896(2)

F(23)-P(20)-F(26) 923(2)

F(21)-P(20)-F(26) 1778(2)

F(23)-P(20)-F(24) 9177(19)

F(21)-P(20)-F(24) 8826(17)

F(26)-P(20)-F(24) 9056(16)

F(23)-P(20)-F(22) 893(2)

F(21)-P(20)-F(22) 9091(19)

F(26)-P(20)-F(22) 9024(18)

F(24)-P(20)-F(22) 1787(2)

F(23)-P(20)-F(25) 1794(2)

F(21)-P(20)-F(25) 908(2)

F(26)-P(20)-F(25) 873(2)

F(24)-P(20)-F(25) 8868(19)

F(22)-P(20)-F(25) 903(2)

C(91)-O(90)-C(93) 1125(6)

O(90)-C(91)-C(92) 1100(6)

C(94)-C(93)-O(90) 1137(7)

C(91)-O(90)-C(93) 119(2)

O(90)-C(91)-C(92) 1157(17)

O(90)-C(93)-C(94) 1167(17)

216










b = 107032(4) Aring = 78500(4)deg

c = 212565(12) Aring = 88333(3)deg




F(000) 946









217









Pd(1)-P(2) 22888(9)

Pd(1)-P(1) 23146(9)

Pd(1)-S(1) 23388(8)

Pd(1)-S(3) 23479(9)

P(1)-C(7) 1816(4)

P(1)-C(13) 1817(3)

P(1)-C(19) 1825(4)

P(2)-C(25) 1809(4)

P(2)-C(37) 1821(4)

P(2)-C(31) 1822(4)

S(1)-C(2) 1727(4)

C(2)-N(4) 1326(4)

C(2)-S(3) 1714(4)

N(4)-C(5) 1463(5)

N(4)-C(6) 1480(5)

C(5)-C(6)1 1519(6)

C(6)-C(5)1 1519(6)

C(7)-C(8) 1398(6)

C(7)-C(12) 1399(5)

C(8)-C(9) 1378(6)

C(9)-C(10) 1379(7)

C(10)-C(11) 1390(8)

C(11)-C(12) 1369(7)

C(13)-C(14) 1386(6)

C(13)-C(18) 1392(5)

C(14)-C(15) 1389(5)

C(15)-C(16) 1380(6)

C(16)-C(17) 1381(7)

C(17)-C(18) 1397(5)

C(19)-C(24) 1383(6)

C(19)-C(20) 1386(6)

C(20)-C(21) 1388(6)

C(21)-C(22) 1375(8)

C(22)-C(23) 1370(9)

C(23)-C(24) 1407(7)

C(25)-C(30) 1394(6)

C(25)-C(26) 1396(6)

C(26)-C(27) 1379(6)

C(27)-C(28) 1384(8)

C(28)-C(29) 1365(8)

C(29)-C(30) 1395(6)

C(31)-C(32) 1389(5)

C(31)-C(36) 1391(5)

C(32)-C(33) 1392(6)

C(33)-C(34) 1377(7)

C(34)-C(35) 1377(6)

C(8)-C(7)-P(1) 1204(3)

C(12)-C(7)-P(1) 1209(3)

C(9)-C(8)-C(7) 1203(4)

C(8)-C(9)-C(10) 1202(5)

C(9)-C(10)-C(11) 1199(5)

C(12)-C(11)-C(10) 1202(4)

C(11)-C(12)-C(7) 1205(4)

C(14)-C(13)-C(18) 1191(3)

C(14)-C(13)-P(1) 1215(3)

C(18)-C(13)-P(1) 1194(3)

C(13)-C(14)-C(15) 1204(4)

C(16)-C(15)-C(14) 1202(4)

C(15)-C(16)-C(17) 1202(4)

C(16)-C(17)-C(18) 1196(4)

C(13)-C(18)-C(17) 1204(4)

C(24)-C(19)-C(20) 1194(4)

C(24)-C(19)-P(1) 1224(3)

C(20)-C(19)-P(1) 1182(3)

C(19)-C(20)-C(21) 1209(5)

C(22)-C(21)-C(20) 1197(5)

C(23)-C(22)-C(21) 1201(5)

C(22)-C(23)-C(24) 1207(5)

C(19)-C(24)-C(23) 1192(5)

C(30)-C(25)-C(26) 1191(4)

C(30)-C(25)-P(2) 1230(3)

C(26)-C(25)-P(2) 1176(3)

C(27)-C(26)-C(25) 1206(4)

C(26)-C(27)-C(28) 1197(5)

C(29)-C(28)-C(27) 1206(4)

C(28)-C(29)-C(30) 1204(5)

C(25)-C(30)-C(29) 1196(4)

C(32)-C(31)-C(36) 1189(4)

C(32)-C(31)-P(2) 1257(3)

C(36)-C(31)-P(2) 1153(3)

C(31)-C(32)-C(33) 1198(4)

C(34)-C(33)-C(32) 1207(4)

C(35)-C(34)-C(33) 1198(4)

C(34)-C(35)-C(36) 1200(4)

C(35)-C(36)-C(31) 1207(4)

C(42)-C(37)-C(38) 1184(4)

C(42)-C(37)-P(2) 1189(3)

C(38)-C(37)-P(2) 1227(3)

C(39)-C(38)-C(37) 1197(5)

C(40)-C(39)-C(38) 1206(5)

C(39)-C(40)-C(41) 1208(5)

C(40)-C(41)-C(42) 1197(5)

218

C(35)-C(36) 1387(6)

C(37)-C(42) 1385(6)

C(37)-C(38) 1399(6)

C(38)-C(39) 1392(6)

C(39)-C(40) 1360(8)

C(40)-C(41) 1361(8)

C(41)-C(42) 1394(7)

P(10)-F(14) 1578(10)

P(10)-F(13) 1579(10)

P(10)-F(16) 1597(10)

P(10)-F(12) 1598(10)

P(10)-F(15) 1599(10)

P(10)-F(11) 1614(10)

P(10)-F(11) 1588(13)

P(10)-F(13) 1591(13)

P(10)-F(14) 1592(13)

P(10)-F(12) 1593(13)

P(10)-F(16) 1595(13)

P(10)-F(15) 1598(13)

P(20)-F(25) 1551(11)

P(20)-F(24) 1557(12)

P(20)-F(26) 1563(11)

P(20)-F(22) 1566(11)

P(20)-F(21) 1575(11)

P(20)-F(23) 1585(11)

P(20)-F(23) 1521(11)

P(20)-F(21) 1545(11)

P(20)-F(26) 1559(11)

P(20)-F(24) 1560(11)

P(20)-F(22) 1585(11)

P(20)-F(25) 1628(11)

P(2)-Pd(1)-P(1) 9715(3)

P(2)-Pd(1)-S(1) 9505(3)

P(1)-Pd(1)-S(1) 16705(3)

P(2)-Pd(1)-S(3) 16837(3)

P(1)-Pd(1)-S(3) 9298(3)

S(1)-Pd(1)-S(3) 7536(3)

C(7)-P(1)-C(13) 10326(17)

C(7)-P(1)-C(19) 10743(19)

C(13)-P(1)-C(19) 10434(17)

C(7)-P(1)-Pd(1) 11069(13)

C(13)-P(1)-Pd(1) 12157(12)

C(19)-P(1)-Pd(1) 10864(13)

C(25)-P(2)-C(37) 10169(18)

C(25)-P(2)-C(31) 11326(17)

C(37)-P(2)-C(31) 10528(17)

C(25)-P(2)-Pd(1) 11377(13)

C(37)-P(2)-Pd(1) 11311(12)

C(31)-P(2)-Pd(1) 10929(13)

C(2)-S(1)-Pd(1) 8589(12)

N(4)-C(2)-S(3) 1233(3)

N(4)-C(2)-S(1) 1239(3)

S(3)-C(2)-S(1) 11276(19)

C(2)-S(3)-Pd(1) 8590(13)

C(2)-N(4)-C(5) 1234(3)

C(2)-N(4)-C(6) 1228(3)

C(5)-N(4)-C(6) 1133(3)

N(4)-C(5)-C(6)1 1090(3)

N(4)-C(6)-C(5)1 1087(3)

C(8)-C(7)-C(12) 1188(4)

C(37)-C(42)-C(41) 1208(4)

F(14)-P(10)-F(13) 910(7)

F(14)-P(10)-F(16) 912(6)

F(13)-P(10)-F(16) 912(6)

F(14)-P(10)-F(12) 1781(8)

F(13)-P(10)-F(12) 901(7)

F(16)-P(10)-F(12) 904(7)

F(14)-P(10)-F(15) 902(7)

F(13)-P(10)-F(15) 1783(8)

F(16)-P(10)-F(15) 901(7)

F(12)-P(10)-F(15) 886(7)

F(14)-P(10)-F(11) 901(7)

F(13)-P(10)-F(11) 894(7)

F(16)-P(10)-F(11) 1785(9)

F(12)-P(10)-F(11) 883(6)

F(15)-P(10)-F(11) 893(6)

F(11)-P(10)-F(13) 904(8)

F(11)-P(10)-F(14) 902(8)

F(13)-P(10)-F(14) 903(8)

F(11)-P(10)-F(12) 902(8)

F(13)-P(10)-F(12) 901(8)

F(14)-P(10)-F(12) 1795(11)

F(11)-P(10)-F(16) 1794(11)

F(13)-P(10)-F(16) 902(8)

F(14)-P(10)-F(16) 899(8)

F(12)-P(10)-F(16) 897(8)

F(11)-P(10)-F(15) 898(8)

F(13)-P(10)-F(15) 1798(12)

F(14)-P(10)-F(15) 899(8)

F(12)-P(10)-F(15) 897(8)

F(16)-P(10)-F(15) 896(8)

F(25)-P(20)-F(24) 911(7)

F(25)-P(20)-F(26) 923(7)

F(24)-P(20)-F(26) 911(7)

F(25)-P(20)-F(22) 916(7)

F(24)-P(20)-F(22) 1766(10)

F(26)-P(20)-F(22) 908(7)

F(25)-P(20)-F(21) 899(7)

F(24)-P(20)-F(21) 902(8)

F(26)-P(20)-F(21) 1774(9)

F(22)-P(20)-F(21) 878(7)

F(25)-P(20)-F(23) 1786(10)

F(24)-P(20)-F(23) 894(7)

F(26)-P(20)-F(23) 890(7)

F(22)-P(20)-F(23) 879(7)

F(21)-P(20)-F(23) 888(7)

F(23)-P(20)-F(21) 941(7)

F(23)-P(20)-F(26) 932(7)

F(21)-P(20)-F(26) 1724(8)

F(23)-P(20)-F(24) 939(7)

F(21)-P(20)-F(24) 907(7)

F(26)-P(20)-F(24) 910(7)

F(23)-P(20)-F(22) 931(7)

F(21)-P(20)-F(22) 887(7)

F(26)-P(20)-F(22) 886(7)

F(24)-P(20)-F(22) 1730(8)

F(23)-P(20)-F(25) 1771(9)

F(21)-P(20)-F(25) 878(7)

F(26)-P(20)-F(25) 849(7)

F(24)-P(20)-F(25) 883(7)

F(22)-P(20)-F(25) 847(6)

219










b = 1085381(18) Aring = 1065109(16)deg

c = 267343(4) Aring = 90deg




F(000) 4112








220











Pd(1)-P(2) 22811(15)

Pd(1)-S(1) 23190(15)

Pd(1)-P(1) 23297(15)

Pd(1)-S(3) 23720(16)

Pd(2)-P(4) 22915(17)

Pd(2)-S(9) 23180(15)

Pd(2)-P(3) 23298(16)

Pd(2)-S(10) 23735(17)

P(1)-C(37) 1820(7)

P(1)-C(25) 1826(7)

P(1)-C(31) 1832(7)

P(2)-C(43) 1814(6)

P(2)-C(49) 1820(6)

P(2)-C(55) 1826(7)

P(3)-C(61) 1832(9)

P(3)-C(67) 1832(7)

P(3)-C(73) 1837(7)

P(4)-C(85) 1815(7)

P(4)-C(79) 1829(7)

P(4)-C(91) 1833(6)

S(1)-C(2) 1715(7)

C(2)-N(4) 1323(8)

C(2)-S(3) 1718(6)

N(4)-C(5) 1470(8)

N(4)-C(11) 1475(8)

C(5)-C(6) 1518(8)

C(6)-N(7) 1487(8)

N(7)-C(8) 1316(9)

N(7)-C(18) 1463(9)

C(8)-S(9) 1722(7)

C(8)-S(10) 1727(7)

C(11)-C(12) 1500(9)

C(12)-C(13) 1376(11)

C(12)-C(17) 1378(10)

C(13)-C(14) 1385(12)

C(14)-C(15) 1393(14)

C(15)-C(16) 1363(14)

C(16)-C(17) 1377(13)

C(18)-C(19) 1510(11)

C(19)-C(24) 1374(12)

C(19)-C(20) 1406(11)

C(20)-C(21) 1390(15)

C(21)-C(22) 1352(18)

C(22)-C(23) 1395(16)

C(79)-P(4)-Pd(2) 1116(2)

C(91)-P(4)-Pd(2) 1124(20

C(2)-S(1)-Pd(1) 859(2)

N(4)-C(2)-S(1) 1227(5)

N(4)-C(2)-S(3) 1240(5)

S(1)-C(2)-S(3) 1132(4)

C(2)-S(3)-Pd(1) 842(2)

C(2)-N(4)-C(5) 1214(5)

C(2)-N(4)-C(11) 1207(5)

C(5)-N(4)-C(11) 1176(5)

N(4)-C(5)-C(6) 1104(5)

N(7)-C(6)-C(5) 1085(5)

C(8)-N(7)-C(18) 1229(6)

C(8)-N(7)-C(6) 1194(6)

C(18)-N(7)-C(6) 1177(5)

N(7)-C(8)-S(9) 1234(5)

N(7)-C(8)-S(10) 1247(5)

S(9)-C(8)-S(10) 1119(4)

C(8)-S(9)-Pd(2) 873(2)

C(8)-S(10)-Pd(2) 854(2)

N(4)-C(11)-C(12) 1154(5)

C(13)-C(12)-C(17) 1187(7)

C(13)-C(12)-C(11) 1218(6)

C(17)-C(12)-C(11) 1193(6)

C(12)-C(13)-C(14) 1206(8)

C(13)-C(14)-C(15) 1203(9)

C(16)-C(15)-C(14) 1185(8)

C(15)-C(16)-C(17) 1214(8)

C(16)-C(17)-C(12) 1206(8)

N(7)-C(18)-C(19) 1127(6)

C(24)-C(19)-C(20) 1180(8)

C(24)-C(19)-C(18) 1234(7)

C(20)-C(19)-C(18) 1185(8)

C(21)-C(20)-C(19) 1189(10)

C(22)-C(21)-C(20) 1229(9)

C(21)-C(22)-C(23) 1187(10)

C(24)-C(23)-C(22) 1193(10)

C(19)-C(24)-C(23) 1222(8)

C(30)-C(25)-C(26) 1194(6)

C(30)-C(25)-P(1) 1211(5)

C(26)-C(25)-P(1) 1194(5)

C(27)-C(26)-C(25) 1195(7)

C(28)-C(27)-C(26) 1206(7)

221

C(23)-C(24) 1389(12)

C(25)-C(30) 1387(10)

C(25)-C(26) 1396(9)

C(26)-C(27) 1392(10)

C(27)-C(28) 1372(12)

C(28)-C(29) 1373(12)

C(29)-C(30) 1391(10)

C(31)-C(32) 1392(9)

C(31)-C(36) 1404(9)

C(32)-C(33) 1390(10)

C(33)-C(34) 1390(13)

C(34)-C(35) 1368(13)

C(35)-C(36) 1396(11)

C(37)-C(42) 1387(10)

C(37)-C(38) 1393(10)

C(38)-C(39) 1387(10)

C(39)-C(40) 1361(12)

C(40)-C(41) 1385(12)

C(41)-C(42) 1390(10)

C(43)-C(48) 1396(10)

C(43)-C(44) 1400(10)

C(44)-C(45) 1370(10)

C(45)-C(46) 1379(12)

C(46)-C(47) 1382(13)

C(47)-C(48) 1400(11)

C(49)-C(54) 1384(11)

C(49)-C(50) 1400(10)

C(50)-C(51) 1380(9)

C(51)-C(52) 1377(14)

C(52)-C(53) 1362(15)

C(53)-C(54) 1399(11)

C(55)-C(60) 1380(9)

C(55)-C(56) 1407(9)

C(56)-C(57) 1370(10)

C(57)-C(58) 1381(11)

C(58)-C(59) 1402(12)

C(59)-C(60) 1373(11)

C(61)-C(62) 1375(11)

C(61)-C(66) 1404(11)

C(62)-C(63) 1395(11)

C(63)-C(64) 1402(14)

C(64)-C(65) 1358(16)

C(65)-C(66) 1377(14)

C(67)-C(68) 1379(11)

C(67)-C(72) 1401(11)

C(68)-C(69) 1386(11)

C(69)-C(70) 1394(14)

C(70)-C(71) 1376(15)

C(71)-C(72) 1391(12)

C(73)-C(78) 1391(11)

C(73)-C(74) 1400(9)

C(74)-C(75) 1393(13)

C(75)-C(76) 1391(14)

C(76)-C(77) 1394(12)

C(77)-C(78) 1384(13)

C(79)-C(84) 1376(11)

C(79)-C(80) 1402(10)

C(80)-C(81) 1399(10)

C(81)-C(82) 1371(13)

C(82)-C(83) 1384(12)

C(83)-C(84) 1379(10)

C(27)-C(28)-C(29) 1202(7)

C(28)-C(29)-C(30) 1202(7)

C(25)-C(30)-C(29) 1201(7)

C(32)-C(31)-C(36) 1189(6)

C(32)-C(31)-P(1) 1203(5)

C(36)-C(31)-P(1) 1208(5)

C(33)-C(32)-C(31) 1208(7)

C(32)-C(33)-C(34) 1204(7)

C(35)-C(34)-C(33) 1187(7)

C(34)-C(35)-C(36) 1224(7)

C(35)-C(36)-C(31) 1188(7)

C(42)-C(37)-C(38) 1181(6)

C(42)-C(37)-P(1) 1194(5)

C(38)-C(37)-P(1) 1224(5)

C(39)-C(38)-C(37) 1210(7)

C(40)-C(39)-C(38) 1202(7)

C(39)-C(40)-C(41) 1200(7)

C(40)-C(41)-C(42) 1200(7)

C(37)-C(42)-C(41) 1206(7)

C(48)-C(43)-C(44) 1199(6)

C(48)-C(43)-P(2) 1250(6)

C(44)-C(43)-P(2) 1151(5)

C(45)-C(44)-C(43) 1201(7)

C(44)-C(45)-C(46) 1205(7)

C(45)-C(46)-C(47) 1202(7)

C(46)-C(47)-C(48) 1204(7)

C(43)-C(48)-C(47) 1189(8)

C(54)-C(49)-C(50) 1205(6)

C(54)-C(49)-P(2) 1209(6)

C(50)-C(49)-P(2) 1185(5)

C(51)-C(50)-C(49) 1197(7)

C(52)-C(51)-C(50) 1198(8)

C(53)-C(52)-C(51) 1205(7)

C(52)-C(53)-C(54) 1213(8)

C(49)-C(54)-C(53) 1181(8)

C(60)-C(55)-C(56) 1188(6)

C(60)-C(55)-P(2) 1235(5)

C(56)-C(55)-P(2) 1177(5)

C(57)-C(56)-C(55) 1198(6)

C(56)-C(57)-C(58) 1213(7)

C(57)-C(58)-C(59) 1190(7)

C(60)-C(59)-C(58) 1197(7)

C(59)-C(60)-C(55) 1213(7)

C(62)-C(61)-C(66) 1196(8)

C(62)-C(61)-P(3) 1193(6)

C(66)-C(61)-P(3) 1208(7)

C(61)-C(62)-C(63) 1218(8)

C(62)-C(63)-C(64) 1176(9)

C(65)-C(64)-C(63) 1203(8)

C(64)-C(65)-C(66) 1224(9)

C(65)-C(66)-C(61) 1183(9)

C(68)-C(67)-C(72) 1195(7)

C(68)-C(67)-P(3) 1198(6)

C(72)-C(67)-P(3) 1204(6)

C(67)-C(68)-C(69) 1210(8)

C(68)-C(69)-C(70) 1192(8)

C(71)-C(70)-C(69) 1205(8)

C(70)-C(71)-C(72) 1202(9)

C(71)-C(72)-C(67) 1196(9)

C(78)-C(73)-C(74) 1186(7)

C(78)-C(73)-P(3) 1212(5)

222

C(85)-C(90) 1379(11)

C(85)-C(86) 1391(10)

C(86)-C(87) 1391(10)

C(87)-C(88) 1387(15)

C(88)-C(89) 1371(14)

C(89)-C(90) 1390(11)

C(91)-C(92) 1379(9)

C(91)-C(96) 1387(9)

C(92)-C(93) 1393(11)

C(93)-C(94) 1368(12)

C(94)-C(95) 1397(11)

C(95)-C(96) 1375(10)

P(10)-F(11) 1550(6)

P(10)-F(15) 1576(5)

P(10)-F(13) 1584(6)

P(10)-F(14) 1590(6)

P(10)-F(12) 1600(5)

P(10)-F(16) 1600(7)

P(20)-F(26) 1543(8)

P(20)-F(21) 1565(8)

P(20)-F(25) 1565(5)

P(20)-F(22) 1568(6)

P(20)-F(24) 1571(6)

P(20)-F(23) 1581(5)

P(2)-Pd(1)-S(1) 9072(5)

P(2)-Pd(1)-P(1) 9793(6)

S(1)-Pd(1)-P(1) 16824(5)

P(2)-Pd(1)-S(3) 16550(6)

S(1)-Pd(1)-S(3) 7528(5)

P(1)-Pd(1)-S(3) 9647(5)

P(4)-Pd(2)-S(9) 9136(5)

P(4)-Pd(2)-P(3) 9795(6)

S(9)-Pd(2)-P(3) 17015(6)

P(4)-Pd(2)-S(10) 16641(6)

S(9)-Pd(2)-S(10) 7505(5)

P(3)-Pd(2)-S(10) 9564(6)

C(37)-P(1)-C(25) 1061(3)

C(37)-P(1)-C(31) 1040(3)

C(25)-P(1)-C(31) 1013(3)

C(37)-P(1)-Pd(1) 1142(2)

C(25)-P(1)-Pd(1) 1091(2)

C(31)-P(1)-Pd(1) 1205(2)

C(43)-P(2)-C(49) 1115(3)

C(43)-P(2)-C(55) 1047(3)

C(49)-P(2)-C(55) 1020(3)

C(43)-P(2)-Pd(1) 1110(2)

C(49)-P(2)-Pd(1) 1132(2)

C(55)-P(2)-Pd(1) 1139(2)

C(61)-P(3)-C(67) 1067(4)

C(61)-P(3)-C(73) 1028(4)

C(67)-P(3)-C(73) 1047(4)

C(61)-P(3)-Pd(2) 1087(3)

C(67)-P(3)-Pd(2) 1122(3)

C(73)-P(3)-Pd(2) 1207(2)

C(85)-P(4)-C(79) 1107(3)

C(85)-P(4)-C(91) 1023(3)

C(79)-P(4)-C(91) 1052(3)

C(85)-P(4)-Pd(2) 1139(3)

C(74)-C(73)-P(3) 1202(6)

C(75)-C(74)-C(73) 1202(8)

C(76)-C(75)-C(74) 1199(7)

C(75)-C(76)-C(77) 1207(8)

C(78)-C(77)-C(76) 1186(9)

C(77)-C(78)-C(73) 1220(7)

C(84)-C(79)-C(80) 1205(6)

C(84)-C(79)-P(4) 1249(5)

C(80)-C(79)-P(4) 1146(5)

C(81)-C(80)-C(79) 1181(7)

C(82)-C(81)-C(80) 1211(7)

C(81)-C(82)-C(83) 1197(7)

C(84)-C(83)-C(82) 1203(7)

C(79)-C(84)-C(83) 1201(7)

C(90)-C(85)-C(86) 1198(7)

C(90)-C(85)-P(4) 1219(6)

C(86)-C(85)-P(4) 1183(6)

C(87)-C(86)-C(85) 1201(8)

C(88)-C(87)-C(86) 1198(8)

C(89)-C(88)-C(87) 1195(7)

C(88)-C(89)-C(90) 1212(9)

C(85)-C(90)-C(89) 1195(8)

C(92)-C(91)-C(96) 1197(6)

C(92)-C(91)-P(4) 1225(5)

C(96)-C(91)-P(4) 1177(5)

C(91)-C(92)-C(93) 1198(7)

C(94)-C(93)-C(92) 1209(7)

C(93)-C(94)-C(95) 1189(7)

C(96)-C(95)-C(94) 1207(7)

C(95)-C(96)-C(91) 1201(6)

F(11)-P(10)-F(15) 920(4)

F(11)-P(10)-F(13) 909(4)

F(15)-P(10)-F(13) 1769(4)

F(11)-P(10)-F(14) 909(4)

F(15)-P(10)-F(14) 889(3)

F(13)-P(10)-F(14) 921(4)

F(11)-P(10)-F(12) 902(4)

F(15)-P(10)-F(12) 897(3)

F(13)-P(10)-F(12) 892(3)

F(14)-P(10)-F(12) 1783(3)

F(11)-P(10)-F(16) 1792(4)

F(15)-P(10)-F(16) 885(4)

F(13)-P(10)-F(16) 885(4)

F(14)-P(10)-F(16) 897(4)

F(12)-P(10)-F(16) 892(3)

F(26)-P(20)-F(21) 1790(6)

F(26)-P(20)-F(25) 893(5)

F(21)-P(20)-F(25) 897(5)

F(26)-P(20)-F(22) 932(6)

F(21)-P(20)-F(22) 865(6)

F(25)-P(20)-F(22) 894(4)

F(26)-P(20)-F(24) 875(6)

F(21)-P(20)-F(24) 928(6)

F(25)-P(20)-F(24) 907(3)

F(22)-P(20)-F(24) 1794(6)

F(26)-P(20)-F(23) 889(4)

F(21)-P(20)-F(23) 921(4)

F(25)-P(20)-F(23) 1780(5)

F(22)-P(20)-F(23) 899(3)

F(24)-P(20)-F(23) 901(3)

223





224




05(C H2 Cl2)






b = 192506(5) Aring = 970520(16)deg

c = 494978(9) Aring = 90deg




F(000) 8880
















225


Pd(1A)-P(2A) 23045(9)

Pd(1A)-P(1A) 23091(9)

Pd(1A)-S(1A) 23294(9)

Pd(1A)-S(3A) 23458(9)

P(1A)-C(22A) 1817(3)

P(1A)-C(28A) 1820(3)

P(1A)-C(16A) 1821(3)

P(1A)-C(22) 1838(8)

P(2A)-C(46A) 1815(4)

P(2A)-C(34A) 1823(4)

P(2A)-C(40A) 1837(4)

P(2A)-C(40) 1843(6)

S(1A)-C(2A) 1726(3)

C(2A)-N(4A) 1306(4)

C(2A)-S(3A) 1717(4)

N(4A)-C(5A) 1467(5)

N(4A)-C(15A) 1467(4)

C(5A)-C(6A) 1528(5)

C(6A)-C(7A) 1512(5)

C(7A)-Si(8A) 1718(5)

C(7A)-Si(8) 2004(6)

Si(8A)-O(13A) 1602(5)

Si(8A)-O(9A) 1629(6)

Si(8A)-O(11A) 1634(5)

O(9A)-C(10A) 1436(8)

O(11A)-C(12A) 1401(8)

O(13A)-C(14A) 1388(9)

Si(8)-O(9) 1606(8)

Si(8)-O(11) 1618(8)

Si(8)-O(13) 1633(8)

O(9)-C(10) 1422(12)

O(11)-C(12) 1418(13)

O(13)-C(14) 1462(12)

C(16A)-C(21A) 1387(5)

C(16A)-C(17A) 1391(5)

C(17A)-C(18A) 1379(5)

C(18A)-C(19A) 1378(6)

C(19A)-C(20A) 1359(6)

C(20A)-C(21A) 1395(5)

C(22A)-C(23A) 13900

C(22A)-C(27A) 13900

C(23A)-C(24A) 13900

C(24A)-C(25A) 13900

C(25A)-C(26A) 13900

C(26A)-C(27A) 13900

C(22)-C(23) 13900

C(22)-C(27) 13900

C(23)-C(24) 13900

C(24)-C(25) 13900

C(25)-C(26) 13900

C(26)-C(27) 13900

C(28A)-C(33A) 1385(5)

C(28A)-C(29A) 1395(5)

C(29A)-C(30A) 1377(5)

C(30A)-C(31A) 1367(6)

C(31A)-C(32A) 1380(6)

C(32A)-C(33A) 1387(5)

C(34A)-C(35A) 1377(5)

C(34A)-C(39A) 1394(5)

O(13)-Si(8)-C(7A) 1101(4)

C(10)-O(9)-Si(8) 1212(8)

C(12)-O(11)-Si(8) 1233(9)

C(14)-O(13)-Si(8) 1224(8)

C(21A)-C(16A)-C(17A) 1189(3)

C(21A)-C(16A)-P(1A) 1232(3)

C(17A)-C(16A)-P(1A) 1178(3)

C(18A)-C(17A)-C(16A) 1206(4)

C(19A)-C(18A)-C(17A) 1198(4)

C(20A)-C(19A)-C(18A) 1205(4)

C(19A)-C(20A)-C(21A) 1203(4)

C(16A)-C(21A)-C(20A) 1198(4)

C(23A)-C(22A)-C(27A) 1200

C(23A)-C(22A)-P(1A) 1187(3)

C(27A)-C(22A)-P(1A) 1213(3)

C(24A)-C(23A)-C(22A) 1200

C(25A)-C(24A)-C(23A) 1200

C(24A)-C(25A)-C(26A) 1200

C(27A)-C(26A)-C(25A) 1200

C(26A)-C(27A)-C(22A) 1200

C(23)-C(22)-C(27) 1200

C(23)-C(22)-P(1A) 1215(7)

C(27)-C(22)-P(1A) 1185(7)

C(24)-C(23)-C(22) 1200

C(25)-C(24)-C(23) 1200

C(24)-C(25)-C(26) 1200

C(25)-C(26)-C(27) 1200

C(26)-C(27)-C(22) 1200

C(33A)-C(28A)-C(29A) 1187(3)

C(33A)-C(28A)-P(1A) 1220(3)

C(29A)-C(28A)-P(1A) 1193(3)

C(30A)-C(29A)-C(28A) 1205(4)

C(31A)-C(30A)-C(29A) 1205(4)

C(30A)-C(31A)-C(32A) 1199(4)

C(31A)-C(32A)-C(33A) 1202(4)

C(28A)-C(33A)-C(32A) 1202(4)

C(35A)-C(34A)-C(39A) 1196(3)

C(35A)-C(34A)-P(2A) 1178(3)

C(39A)-C(34A)-P(2A) 1226(3)

C(34A)-C(35A)-C(36A) 1199(4)

C(37A)-C(36A)-C(35A) 1198(5)

C(38A)-C(37A)-C(36A) 1203(4)

C(37A)-C(38A)-C(39A) 1204(4)

C(38A)-C(39A)-C(34A) 1200(4)

C(41A)-C(40A)-C(45A) 1200

C(41A)-C(40A)-P(2A) 1219(4)

C(45A)-C(40A)-P(2A) 1181(4)

C(42A)-C(41A)-C(40A) 1200

C(41A)-C(42A)-C(43A) 1200

C(42A)-C(43A)-C(44A) 1200

C(45A)-C(44A)-C(43A) 1200

C(44A)-C(45A)-C(40A) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2A) 1242(5)

C(45)-C(40)-P(2A) 1152(6)

C(40)-C(41)-C(42) 1200

C(43)-C(42)-C(41) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

226

C(35A)-C(36A) 1394(6)

C(36A)-C(37A) 1377(7)

C(37A)-C(38A) 1369(7)

C(38A)-C(39A) 1374(5)

C(40A)-C(41A) 13900

C(40A)-C(45A) 13900

C(41A)-C(42A) 13900

C(42A)-C(43A) 13900

C(43A)-C(44A) 13900

C(44A)-C(45A) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46A)-C(51A) 1374(5)

C(46A)-C(47A) 1390(5)

C(47A)-C(48A) 1378(5)

C(48A)-C(49A) 1366(6)

C(49A)-C(50A) 1372(6)

C(50A)-C(51A) 1397(5)

Pd(1B)-P(2B) 22980(9)

Pd(1B)-P(1B) 23261(9)

Pd(1B)-S(1B) 23293(9)

Pd(1B)-S(3B) 23476(10)

P(1B)-C(28) 1800(6)

P(1B)-C(22B) 1817(3)

P(1B)-C(16B) 1822(3)

P(1B)-C(28B) 1853(3)

P(2B)-C(46B) 1725(3)

P(2B)-C(40) 1811(7)

P(2B)-C(34B) 1819(4)

P(2B)-C(40B) 1849(4)

P(2B)-C(46) 1911(5)

S(1B)-C(2B) 1719(4)

C(2B)-N(4B) 1312(5)

C(2B)-S(3B) 1722(4)

N(4B)-C(15B) 1434(7)

N(4B)-C(5) 1434(11)

N(4B)-C(5B) 1523(9)

N(4B)-C(15) 1553(9)

C(5B)-C(6B) 1527(11)

C(6B)-C(7B) 1513(9)

C(7B)-Si(8B) 1842(7)

Si(8B)-O(11B) 1612(6)

Si(8B)-O(9B) 1626(8)

Si(8B)-O(13B) 1629(5)

O(9B)-C(10B) 1426(12)

O(11B)-C(12B) 1431(10)

O(13B)-C(14B) 1383(10)

C(5)-C(6) 1496(12)

C(6)-C(7) 1488(10)

C(7)-Si(8) 1861(8)

Si(8)-O(9) 1577(9)

Si(8)-O(13) 1600(8)

Si(8)-O(11) 1640(8)

O(9)-C(10) 1372(13)

O(11)-C(12) 1411(10)

O(13)-C(14) 1388(12)

C(16B)-C(17B) 1369(5)

C(44)-C(45)-C(40) 1200

C(51A)-C(46A)-C(47A) 1192(3)

C(51A)-C(46A)-P(2A) 1215(3)

C(47A)-C(46A)-P(2A) 1194(3)

C(48A)-C(47A)-C(46A) 1205(4)

C(49A)-C(48A)-C(47A) 1200(4)

C(48A)-C(49A)-C(50A) 1203(4)

C(49A)-C(50A)-C(51A) 1200(4)

C(46A)-C(51A)-C(50A) 1200(4)

P(2B)-Pd(1B)-P(1B) 9991(3)

P(2B)-Pd(1B)-S(1B) 9282(3)

P(1B)-Pd(1B)-S(1B) 16611(3)

P(2B)-Pd(1B)-S(3B) 16751(4)

P(1B)-Pd(1B)-S(3B) 9257(3)

S(1B)-Pd(1B)-S(3B) 7472(4)

C(28)-P(1B)-C(22B) 1115(3)

C(28)-P(1B)-C(16B) 1024(4)

C(22B)-P(1B)-C(16B) 10549(16)

C(22B)-P(1B)-C(28B) 1015(2)

C(16B)-P(1B)-C(28B) 1044(2)

C(28)-P(1B)-Pd(1B) 1174(3)

C(22B)-P(1B)-Pd(1B) 10938(12)

C(16B)-P(1B)-Pd(1B) 10984(12)

C(28B)-P(1B)-Pd(1B) 1245(2)

C(46B)-P(2B)-C(34B) 1031(2)

C(40)-P(2B)-C(34B) 1057(4)

C(46B)-P(2B)-C(40B) 1035(3)

C(34B)-P(2B)-C(40B) 1050(2)

C(40)-P(2B)-C(46) 994(5)

C(34B)-P(2B)-C(46) 1146(3)

C(46B)-P(2B)-Pd(1B) 12210(18)

C(40)-P(2B)-Pd(1B) 1163(4)

C(34B)-P(2B)-Pd(1B) 11240(13)

C(40B)-P(2B)-Pd(1B) 1092(3)

C(46)-P(2B)-Pd(1B) 10795(19)

C(2B)-S(1B)-Pd(1B) 8727(14)

N(4B)-C(2B)-S(1B) 1242(3)

N(4B)-C(2B)-S(3B) 1247(3)

S(1B)-C(2B)-S(3B) 1111(2)

C(2B)-S(3B)-Pd(1B) 8661(13)

C(2B)-N(4B)-C(15B) 1252(5)

C(2B)-N(4B)-C(5) 1241(9)

C(2B)-N(4B)-C(5B) 1207(6)

C(15B)-N(4B)-C(5B) 1135(6)

C(2B)-N(4B)-C(15) 1156(5)

C(5)-N(4B)-C(15) 1200(9)

N(4B)-C(5B)-C(6B) 1098(7)

C(7B)-C(6B)-C(5B) 1152(7)

C(6B)-C(7B)-Si(8B) 1124(5)

O(11B)-Si(8B)-O(9B) 1112(4)

O(11B)-Si(8B)-O(13B) 1081(3)

O(9B)-Si(8B)-O(13B) 1049(4)

O(11B)-Si(8B)-C(7B) 1091(3)

O(9B)-Si(8B)-C(7B) 1110(4)

O(13B)-Si(8B)-C(7B) 1124(3)

C(10B)-O(9B)-Si(8B) 1228(7)

C(12B)-O(11B)-Si(8B) 1249(6)

C(14B)-O(13B)-Si(8B) 1273(7)

N(4B)-C(5)-C(6) 1110(10)

C(7)-C(6)-C(5) 1143(10)

C(6)-C(7)-Si(8) 1165(7)

227

C(16B)-C(21B) 1378(5)

C(17B)-C(18B) 1386(5)

C(18B)-C(19B) 1359(6)

C(19B)-C(20B) 1360(6)

C(20B)-C(21B) 1384(5)

C(22B)-C(23B) 1383(5)

C(22B)-C(27B) 1385(5)

C(23B)-C(24B) 1384(6)

C(24B)-C(25B) 1362(7)

C(25B)-C(26B) 1364(7)

C(26B)-C(27B) 1373(5)

C(28B)-C(29B) 13900

C(28B)-C(33B) 13900

C(29B)-C(30B) 13900

C(30B)-C(31B) 13900

C(31B)-C(32B) 13900

C(32B)-C(33B) 13900

C(28)-C(29) 13900

C(28)-C(33) 13900

C(29)-C(30) 13900

C(30)-C(31) 13900

C(31)-C(32) 13900

C(32)-C(33) 13900

C(34B)-C(35B) 1381(6)

C(34B)-C(39B) 1396(6)

C(35B)-C(36B) 1394(6)

C(36B)-C(37B) 1388(7)

C(37B)-C(38B) 1363(8)

C(38B)-C(39B) 1383(7)

C(40B)-C(41B) 13900

C(40B)-C(45B) 13900

C(41B)-C(42B) 13900

C(42B)-C(43B) 13900

C(43B)-C(44B) 13900

C(44B)-C(45B) 13900

C(40)-C(41) 13900

C(40)-C(45) 13900

C(41)-C(42) 13900

C(42)-C(43) 13900

C(43)-C(44) 13900

C(44)-C(45) 13900

C(46B)-C(47B) 13900

C(46B)-C(51B) 13900

C(47B)-C(48B) 13900

C(48B)-C(49B) 13900

C(49B)-C(50B) 13900

C(50B)-C(51B) 13900

C(46)-C(47) 13900

C(46)-C(51) 13900

C(47)-C(48) 13900

C(48)-C(49) 13900

C(49)-C(50) 13900

C(50)-C(51) 13900

P(60)-F(65) 1563(4)

P(60)-F(62) 1570(4)

P(60)-F(64) 1572(4)

P(60)-F(63) 1581(4)

P(60)-F(66) 1592(4)

P(60)-F(61) 1601(4)

P(60)-F(62) 1557(11)

P(60)-F(64) 1562(11)

O(9)-Si(8)-O(13) 1091(6)

O(9)-Si(8)-O(11) 1115(5)

O(13)-Si(8)-O(11) 1066(4)

O(9)-Si(8)-C(7) 1042(6)

O(13)-Si(8)-C(7) 1119(4)

O(11)-Si(8)-C(7) 1135(4)

C(10)-O(9)-Si(8) 1269(9)

C(12)-O(11)-Si(8) 1245(7)

C(14)-O(13)-Si(8) 1277(8)

C(17B)-C(16B)-C(21B) 1181(3)

C(17B)-C(16B)-P(1B) 1190(3)

C(21B)-C(16B)-P(1B) 1229(3)

C(16B)-C(17B)-C(18B) 1213(4)

C(19B)-C(18B)-C(17B) 1199(4)

C(18B)-C(19B)-C(20B) 1197(4)

C(19B)-C(20B)-C(21B) 1206(4)

C(16B)-C(21B)-C(20B) 1204(4)

C(23B)-C(22B)-C(27B) 1181(3)

C(23B)-C(22B)-P(1B) 1225(3)

C(27B)-C(22B)-P(1B) 1194(3)

C(22B)-C(23B)-C(24B) 1204(4)

C(25B)-C(24B)-C(23B) 1204(4)

C(24B)-C(25B)-C(26B) 1198(4)

C(25B)-C(26B)-C(27B) 1203(4)

C(26B)-C(27B)-C(22B) 1209(4)

C(29B)-C(28B)-C(33B) 1200

C(29B)-C(28B)-P(1B) 1201(3)

C(33B)-C(28B)-P(1B) 1199(3)

C(28B)-C(29B)-C(30B) 1200

C(31B)-C(30B)-C(29B) 1200

C(30B)-C(31B)-C(32B) 1200

C(31B)-C(32B)-C(33B) 1200

C(32B)-C(33B)-C(28B) 1200

C(29)-C(28)-C(33) 1200

C(29)-C(28)-P(1B) 1209(5)

C(33)-C(28)-P(1B) 1190(5)

C(30)-C(29)-C(28) 1200

C(29)-C(30)-C(31) 1200

C(30)-C(31)-C(32) 1200

C(33)-C(32)-C(31) 1200

C(32)-C(33)-C(28) 1200

C(35B)-C(34B)-C(39B) 1196(4)

C(35B)-C(34B)-P(2B) 1173(3)

C(39B)-C(34B)-P(2B) 1230(4)

C(34B)-C(35B)-C(36B) 1205(4)

C(37B)-C(36B)-C(35B) 1192(5)

C(38B)-C(37B)-C(36B) 1202(5)

C(37B)-C(38B)-C(39B) 1213(5)

C(38B)-C(39B)-C(34B) 1191(5)

C(41B)-C(40B)-C(45B) 1200

C(41B)-C(40B)-P(2B) 1245(4)

C(45B)-C(40B)-P(2B) 1153(4)

C(40B)-C(41B)-C(42B) 1200

C(43B)-C(42B)-C(41B) 1200

C(44B)-C(43B)-C(42B) 1200

C(43B)-C(44B)-C(45B) 1200

C(44B)-C(45B)-C(40B) 1200

C(41)-C(40)-C(45) 1200

C(41)-C(40)-P(2B) 1183(7)

C(45)-C(40)-P(2B) 1217(7)

C(42)-C(41)-C(40) 1200

228

P(60)-F(63) 1568(11)

P(60)-F(65) 1571(11)

P(60)-F(61) 1585(11)

P(60)-F(66) 1605(11)

P(70)-F(73) 1564(3)

P(70)-F(71) 1570(3)

P(70)-F(74) 1570(3)

P(70)-F(75) 1577(3)

P(70)-F(72) 1586(3)

P(70)-F(76) 1592(3)

C(80)-Cl(82) 1647(11)

C(80)-Cl(81) 1747(11)

C(90)-Cl(92) 165(5)

C(90)-Cl(91) 185(7)

P(2A)-Pd(1A)-P(1A) 10199(3)

P(2A)-Pd(1A)-S(1A) 9315(3)

P(1A)-Pd(1A)-S(1A) 16444(3)

P(2A)-Pd(1A)-S(3A) 16753(3)

P(1A)-Pd(1A)-S(3A) 8973(3)

S(1A)-Pd(1A)-S(3A) 7492(3)

C(22A)-P(1A)-C(28A) 1062(2)

C(22A)-P(1A)-C(16A) 1044(2)

C(28A)-P(1A)-C(16A) 10468(16)

C(28A)-P(1A)-C(22) 960(5)

C(16A)-P(1A)-C(22) 1101(5)

C(22A)-P(1A)-Pd(1A) 10918(18)

C(28A)-P(1A)-Pd(1A) 12376(11)

C(16A)-P(1A)-Pd(1A) 10703(12)

C(22)-P(1A)-Pd(1A) 1144(4)

C(46A)-P(2A)-C(34A) 10586(16)

C(46A)-P(2A)-C(40A) 989(3)

C(34A)-P(2A)-C(40A) 1086(3)

C(46A)-P(2A)-C(40) 1060(4)

C(34A)-P(2A)-C(40) 1032(4)

C(46A)-P(2A)-Pd(1A) 11826(12)

C(34A)-P(2A)-Pd(1A) 11366(12)

C(40A)-P(2A)-Pd(1A) 1103(3)

C(40)-P(2A)-Pd(1A) 1086(4)

C(2A)-S(1A)-Pd(1A) 8685(13)

N(4A)-C(2A)-S(3A) 1252(3)

N(4A)-C(2A)-S(1A) 1234(3)

S(3A)-C(2A)-S(1A) 1114(2)

C(2A)-S(3A)-Pd(1A) 8652(12)

C(2A)-N(4A)-C(5A) 1217(3)

C(2A)-N(4A)-C(15A) 1220(3)

C(5A)-N(4A)-C(15A) 1162(3)

N(4A)-C(5A)-C(6A) 1100(3)

C(7A)-C(6A)-C(5A) 1121(3)

C(6A)-C(7A)-Si(8A) 1149(3)

C(6A)-C(7A)-Si(8) 1142(3)

O(13A)-Si(8A)-O(9A) 1067(3)

O(13A)-Si(8A)-O(11A) 1115(3)

O(9A)-Si(8A)-O(11A) 1063(3)

O(13A)-Si(8A)-C(7A) 1115(3)

O(9A)-Si(8A)-C(7A) 1113(3)

O(11A)-Si(8A)-C(7A) 1093(3)

C(10A)-O(9A)-Si(8A) 1226(5)

C(12A)-O(11A)-Si(8A) 1220(5)

C(14A)-O(13A)-Si(8A) 1221(6)

O(9)-Si(8)-O(11) 1128(5)

C(41)-C(42)-C(43) 1200

C(44)-C(43)-C(42) 1200

C(43)-C(44)-C(45) 1200

C(44)-C(45)-C(40) 1200

C(47B)-C(46B)-C(51B) 1200

C(47B)-C(46B)-P(2B) 1224(3)

C(51B)-C(46B)-P(2B) 1176(3)

C(46B)-C(47B)-C(48B) 1200

C(47B)-C(48B)-C(49B) 1200

C(50B)-C(49B)-C(48B) 1200

C(49B)-C(50B)-C(51B) 1200

C(50B)-C(51B)-C(46B) 1200

C(47)-C(46)-C(51) 1200

C(47)-C(46)-P(2B) 1201(3)

C(51)-C(46)-P(2B) 1199(3)

C(48)-C(47)-C(46) 1200

C(49)-C(48)-C(47) 1200

C(50)-C(49)-C(48) 1200

C(49)-C(50)-C(51) 1200

C(50)-C(51)-C(46) 1200

F(65)-P(60)-F(62) 921(3)

F(65)-P(60)-F(64) 890(3)

F(62)-P(60)-F(64) 1789(4)

F(65)-P(60)-F(63) 1788(3)

F(62)-P(60)-F(63) 887(3)

F(64)-P(60)-F(63) 902(3)

F(65)-P(60)-F(66) 899(3)

F(62)-P(60)-F(66) 900(3)

F(64)-P(60)-F(66) 903(3)

F(63)-P(60)-F(66) 910(3)

F(65)-P(60)-F(61) 901(3)

F(62)-P(60)-F(61) 893(3)

F(64)-P(60)-F(61) 903(3)

F(63)-P(60)-F(61) 890(3)

F(66)-P(60)-F(61) 1793(4)

F(62)-P(60)-F(64) 1789(9)

F(62)-P(60)-F(63) 890(7)

F(64)-P(60)-F(63) 910(7)

F(62)-P(60)-F(65) 896(7)

F(64)-P(60)-F(65) 904(7)

F(63)-P(60)-F(65) 1783(9)

F(62)-P(60)-F(61) 904(7)

F(64)-P(60)-F(61) 907(7)

F(63)-P(60)-F(61) 901(7)

F(65)-P(60)-F(61) 909(7)

F(62)-P(60)-F(66) 901(7)

F(64)-P(60)-F(66) 888(7)

F(63)-P(60)-F(66) 893(7)

F(65)-P(60)-F(66) 897(7)

F(61)-P(60)-F(66) 1792(10)

F(73)-P(70)-F(71) 910(2)

F(73)-P(70)-F(74) 912(2)

F(71)-P(70)-F(74) 8971(19)

F(73)-P(70)-F(75) 1774(2)

F(71)-P(70)-F(75) 8995(18)

F(74)-P(70)-F(75) 913(2)

F(73)-P(70)-F(72) 898(2)

F(71)-P(70)-F(72) 9080(18)

F(74)-P(70)-F(72) 1789(2)

F(75)-P(70)-F(72) 8775(19)

F(73)-P(70)-F(76) 8966(18)

229

O(9)-Si(8)-O(13) 1017(5)

O(11)-Si(8)-O(13) 1130(5)

O(9)-Si(8)-C(7A) 1118(5)

O(11)-Si(8)-C(7A) 1074(4)

F(71)-P(70)-F(76) 1790(2)

F(74)-P(70)-F(76) 8954(17)

F(75)-P(70)-F(76) 8944(18)

F(72)-P(70)-F(76) 8994(17)

Cl(82)-C(80)-Cl(81) 1144(7)

Cl(92)-C(90)-Cl(91) 1077(16)











230

b = 147655(6) Aring = 76579(4)deg

c = 162359(7) Aring = 81131(3)deg




F(000) 1228

















Pd(1)-P(2) 22919(8)

Pd(1)-P(1) 23209(8)

Pd(1)-S(1) 23312(8)

Pd(1)-S(3) 23603(8)

P(1)-C(37) 1818(3)

P(1)-C(31) 1820(4)

P(1)-C(25) 1823(4)

P(2)-C(43) 1813(4)

P(2)-C(55) 1820(4)

P(2)-C(49) 1834(3)

S(1)-C(2) 1724(4)

C(2)-N(4) 1310(5)

C(2)-S(3) 1724(3)

N(4)-C(15) 1475(5)

N(4)-C(5) 1483(5)

C(5)-C(6) 1505(6)

C(6)-C(7) 1489(7)

C(7)-Si(8) 1873(5)

Si(8)-O(11) 1496(7)

Si(8)-O(13) 1557(11)

Si(8)-O(9) 1565(12)

Si(8)-O(9) 1624(6)

Si(8)-O(13) 1633(5)

S(3)-C(2)-S(1) 11213(19)

C(2)-S(3)-Pd(1) 8590(12)

C(2)-N(4)-C(15) 1217(3)

C(2)-N(4)-C(5) 1206(3)

C(15)-N(4)-C(5) 1177(3)

N(4)-C(5)-C(6) 1148(4)

C(7)-C(6)-C(5) 1142(4)

C(6)-C(7)-Si(8) 1144(3)

O(13)-Si(8)-O(9) 1104(10)

O(11)-Si(8)-O(9) 1059(5)

O(11)-Si(8)-O(13) 1110(3)

O(9)-Si(8)-O(13) 1031(4)

O(13)-Si(8)-O(11) 1029(7)

O(9)-Si(8)-O(11) 1063(8)

O(11)-Si(8)-C(7) 1136(3)

O(13)-Si(8)-C(7) 1206(7)

O(9)-Si(8)-C(7) 1088(12)

O(9)-Si(8)-C(7) 1139(6)

O(13)-Si(8)-C(7) 1089(3)

O(11)-Si(8)-C(7) 1069(7)

C(10)-O(9)-Si(8) 1278(8)

C(12)-O(11)-Si(8) 1307(7)

C(14)-O(13)-Si(8) 1264(7)

231

Si(8)-O(11) 1664(11)

O(9)-C(10) 1395(9)

O(11)-C(12) 1457(8)

O(13)-C(14) 1401(9)

O(9)-C(10) 1410(13)

O(11)-C(12) 1438(14)

O(13)-C(14) 1399(14)

C(15)-C(16) 1517(5)

C(16)-C(17) 1540(6)

C(17)-Si(18) 1853(5)

Si(18)-O(19) 1609(4)

Si(18)-O(21) 1614(4)

Si(18)-O(23) 1620(13)

Si(18)-O(23) 1636(5)

Si(18)-O(19) 1649(13)

Si(18)-O(21) 1658(14)

O(19)-C(20) 1413(8)

O(21)-C(22) 1370(9)

O(23)-C(24) 1359(9)

O(19)-C(20) 1398(16)

O(21)-C(22) 1396(17)

O(23)-C(24) 1392(16)

C(25)-C(26) 1393(5)

C(25)-C(30) 1399(5)

C(26)-C(27) 1388(6)

C(27)-C(28) 1372(7)

C(28)-C(29) 1376(7)

C(29)-C(30) 1395(6)

C(31)-C(32) 1388(5)

C(31)-C(36) 1397(5)

C(32)-C(33) 1389(5)

C(33)-C(34) 1383(6)

C(34)-C(35) 1391(5)

C(35)-C(36) 1383(5)

C(37)-C(38) 1395(5)

C(37)-C(42) 1397(5)

C(38)-C(39) 1382(5)

C(39)-C(40) 1393(6)

C(40)-C(41) 1380(6)

C(41)-C(42) 1383(5)

C(43)-C(44) 1387(5)

C(43)-C(48) 1399(5)

C(44)-C(45) 1393(5)

C(45)-C(46) 1383(6)

C(46)-C(47) 1383(6)

C(47)-C(48) 1389(5)

C(49)-C(50) 1384(5)

C(49)-C(54) 1404(5)

C(50)-C(51) 1396(6)

C(51)-C(52) 1377(7)

C(52)-C(53) 1384(7)

C(53)-C(54) 1394(5)

C(55)-C(60) 1391(5)

C(55)-C(56) 1394(5)

C(56)-C(57) 1384(6)

C(57)-C(58) 1386(7)

C(58)-C(59) 1382(7)

C(59)-C(60) 1392(6)

P(3)-F(6) 1588(3)

P(3)-F(5) 1590(3)

P(3)-F(3) 1591(3)

C(10)-O(9)-Si(8) 1321(16)

C(12)-O(11)-Si(8) 1203(13)

C(14)-O(13)-Si(8) 1323(16)

N(4)-C(15)-C(16) 1126(3)

C(15)-C(16)-C(17) 1103(3)

C(16)-C(17)-Si(18) 1159(3)

O(19)-Si(18)-O(21) 1125(4)

O(19)-Si(18)-O(23) 1106(3)

O(21)-Si(18)-O(23) 1077(3)

O(23)-Si(18)-O(19) 1101(10)

O(23)-Si(18)-O(21) 1067(11)

O(19)-Si(18)-O(21) 1059(10)

O(19)-Si(18)-C(17) 1084(2)

O(21)-Si(18)-C(17) 1107(4)

O(23)-Si(18)-C(17) 1215(11)

O(23)-Si(18)-C(17) 1068(3)

O(19)-Si(18)-C(17) 1003(9)

O(21)-Si(18)-C(17) 1112(16)

C(20)-O(19)-Si(18) 1270(6)

C(22)-O(21)-Si(18) 1283(6)

C(24)-O(23)-Si(18) 1306(7)

C(20)-O(19)-Si(18) 1250(17)

C(22)-O(21)-Si(18) 1231(18)

C(24)-O(23)-Si(18) 1266(19)

C(26)-C(25)-C(30) 1189(4)

C(26)-C(25)-P(1) 1195(3)

C(30)-C(25)-P(1) 1215(3)

C(27)-C(26)-C(25) 1204(4)

C(28)-C(27)-C(26) 1209(4)

C(27)-C(28)-C(29) 1191(4)

C(28)-C(29)-C(30) 1215(4)

C(29)-C(30)-C(25) 1192(4)

C(32)-C(31)-C(36) 1202(3)

C(32)-C(31)-P(1) 1202(3)

C(36)-C(31)-P(1) 1195(3)

C(31)-C(32)-C(33) 1193(3)

C(34)-C(33)-C(32) 1206(3)

C(33)-C(34)-C(35) 1201(3)

C(36)-C(35)-C(34) 1198(3)

C(35)-C(36)-C(31) 1201(3)

C(38)-C(37)-C(42) 1186(3)

C(38)-C(37)-P(1) 1181(3)

C(42)-C(37)-P(1) 1233(3)

C(39)-C(38)-C(37) 1207(3)

C(38)-C(39)-C(40) 1204(4)

C(41)-C(40)-C(39) 1189(4)

C(40)-C(41)-C(42) 1212(4)

C(41)-C(42)-C(37) 1201(4)

C(44)-C(43)-C(48) 1197(3)

C(44)-C(43)-P(2) 1250(3)

C(48)-C(43)-P(2) 1153(3)

C(43)-C(44)-C(45) 1194(4)

C(46)-C(45)-C(44) 1208(4)

C(45)-C(46)-C(47) 1200(4)

C(46)-C(47)-C(48) 1198(4)

C(47)-C(48)-C(43) 1203(4)

C(50)-C(49)-C(54) 1194(3)

C(50)-C(49)-P(2) 1226(3)

C(54)-C(49)-P(2) 1179(3)

C(49)-C(50)-C(51) 1203(4)

C(52)-C(51)-C(50) 1201(4)

232

P(3)-F(4) 1591(3)

P(3)-F(1) 1591(3)

P(3)-F(2) 1606(3)

P(2)-Pd(1)-P(1) 9913(3)

P(2)-Pd(1)-S(1) 9341(3)

P(1)-Pd(1)-S(1) 16715(3)

P(2)-Pd(1)-S(3) 16839(3)

P(1)-Pd(1)-S(3) 9221(3)

S(1)-Pd(1)-S(3) 7514(3)

C(37)-P(1)-C(31) 10350(15)

C(37)-P(1)-C(25) 10696(16)

C(31)-P(1)-C(25) 10397(16)

C(37)-P(1)-Pd(1) 12280(11)

C(31)-P(1)-Pd(1) 11250(11)

C(25)-P(1)-Pd(1) 10556(11)

C(43)-P(2)-C(55) 11078(16)

C(43)-P(2)-C(49) 10469(16)

C(55)-P(2)-C(49) 10265(16)

C(43)-P(2)-Pd(1) 10997(12)

C(55)-P(2)-Pd(1) 11546(12)

C(49)-P(2)-Pd(1) 11259(11)

C(2)-S(1)-Pd(1) 8681(12)

N(4)-C(2)-S(3) 1239(3)

N(4)-C(2)-S(1) 1239(3)

C(51)-C(52)-C(53) 1203(4)

C(52)-C(53)-C(54) 1200(4)

C(53)-C(54)-C(49) 1198(4)

C(60)-C(55)-C(56) 1195(3)

C(60)-C(55)-P(2) 1194(3)

C(56)-C(55)-P(2) 1210(3)

C(57)-C(56)-C(55) 1198(4)

C(56)-C(57)-C(58) 1207(4)

C(59)-C(58)-C(57) 1197(4)

C(58)-C(59)-C(60) 1201(4)

C(55)-C(60)-C(59) 1202(4)

F(6)-P(3)-F(5) 8938(18)

F(6)-P(3)-F(3) 9022(16)

F(5)-P(3)-F(3) 1796(2)

F(6)-P(3)-F(4) 9002(16)

F(5)-P(3)-F(4) 9024(18)

F(3)-P(3)-F(4) 8977(16)

F(6)-P(3)-F(1) 17916(19)

F(5)-P(3)-F(1) 913(2)

F(3)-P(3)-F(1) 8906(18)

F(4)-P(3)-F(1) 904(2)

F(6)-P(3)-F(2) 8873(16)

F(5)-P(3)-F(2) 9101(19)

F(3)-P(3)-F(2) 8896(16)

F(4)-P(3)-F(2) 1782(2)

F(1)-P(3)-F(2) 908(2)

233



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