G.A. Razuvaev Institute of Organometallic Chemistry of RAS ... · International conference “Topical Problems of Organometallic and Coordination Chemistry” September 3-9, 2010,

International conference “Topical Problems of Organometallic and Coordination Chemistry” September 3-9, 2010, N. Novgorod, Russia

G.A. Razuvaev Institute of Organometallic Chemistry of RAS, Chemistry and Material Science Division of RAS

Scientific Council on Organic and Elementoorganic Chemistry of RAS Russian Foundation for Basic Research

N.I. Lobachevsky Nizhny Novgorod State University Nizhny Novgorod Science Center of RAS

INTERNATIONAL CONFERENCE «TOPICAL PROBLEMS OF ORGANOMETALLIC

AND COORDINATION CHEMISTRY» V RAZUVAEV LECTURES

Book of Abstracts

The conference is supported by

Bruker Ltd. (ООО «Брукер»)

September 3-9, 2010

Volga and Kama rivers Nizhny Novgorod – Elabuga – Ulyanovsk - Nizhny Novgorod, Russia


Organizing committee:

Gleb A. Abakumov (Chairman), Sergey M. Aldoshin, Mikhail Yu. Antipin, Irina P. Beletskaya, Mikhail N. Bochkarev, Vladimir I. Bregadze, Yury N. Bubnov, Anatoly L.

Buchachenko, Vadim Yu. Kukushkin, Vladimir K. Cherkasov (Vice Chairman), Oleg N. Chupahin, Viktor A. Dodonov, Georgy A. Domrachev, Dmitry F.Grishin, Mikhail P. Egorov,

Igor L. Eremenko, Alexandr I. Konovalov, Ilya I. Moiseev, Aziz M. Muzafarov, Oleg M. Nefedov, Elena S. Shubina, Klara G. Shalnova (Scientific Secretary), Oleg G. Sinyashin.

Program committee:

Gleb.A. Abakumov (chairman), Irina P. Beletskaya, Mikhail N. Bochkarev, Vladimir I.

Bregadze, Yury N. Bubnov, Vladimir K. Cherkasov, Dmitry F. Grishin, Mikhail P. Egorov, Elena S. Shubina, Oleg G. Sinyashin

Travel itinerary:


Plenary lectures


PL1

NANOSIZED CATALYTIC SYSTEMS IN ORGANOMETALLIC AND ORGANIC CATALYSIS

I.P. Beletskaya

Moscow State University, 119991, Leninskie Gory, Moscow, RUSSIA

In the lecture two topics will be considered:

1. the problem of leaching and recycling of organometallic and organic catalysts; 2. cross-coupling reactions for carbon-heteroatom (C-P, C-S, C-Se, C-N) bond

formation. e-mail: [email protected]


PL2

NOVEL TRANSITION METAL-CATALYZED METHODS FOR SYNTHESIS AND FUNCTIONALIZATION OF ARENES AND HETEROARENES

V. Gevorgyana

aDepartment of Chemistry, University of Illinois at Chicago, Chicago, Illinois USA

A set of novel efficient transition metal-catalyzed methodologies for synthesis of multisubstituted carbo- and heterocycles has been developed [1-7]. Commonly, regioselective synthesis of carbo- and heterocycles possessing various functional groups is not a trivial task. We have shown, however, that incorporation of migrating step(s) in the cyclization cascade often helps solving this problem. Thus, it was found that in the presence of Cu-, Ag-, and Au catalysts, a number of groups, such as Hal-, RS-, AcO-, TsO-, Ar-, and SiR3 could undergo 1,2- or 1,3-migration, or in some cases even double migration, which allows for expeditious synthesis of densely-functionalized carbo- and heterocycles, which are not easily accessible via existing techniques. We have also explored a direct Pd-catalyzed C-H functionalization approach toward synthesis of multisubstituted aromatic and heteroaromatic molecules [8-11]. Thus, a novel silicon-tether approach for the Pd-catalyzed C-H arylation of phenols has been developed. Next development involved employment of the PyDipSi-, a Si-tethered directing group in the Pd-catalyzed C-H acyloxylation and halogenation reactions. The PyDipSi group is traceless or can easily be converted into a variety of useful functionalities. The scope of these transformations will be demonstrated and the mechanisms will be discussed. [1] J. T. Kim, A. V. Kel'in, V. Gevorgyan, Angew. Chem., Int. Ed. 2003, 42, 98-101. [2] A. W. Sromek, A. V. Kel’in, V. Gevorgyan, Angew. Chem., Int. Ed. 2004, 43, 2280-2282. [3] A. W. Sromek, M. Rubina, V. Gevorgyan, J. Am. Chem. Soc. 2005, 127, 10500-10501. [4] A. S. Dudnik, V. Gevorgyan, Angew. Chem., Int. Ed. 2007, 46, 5195-5197. [5] T. Schwier, A. W. Sromek, D. L. M. Yap, D. Chernyak, V. Gevorgyan, J. Am. Chem. Soc. 2007, 129, 9868-

9878. [6] A. S. Dudnik, A. W. Sromek, M. Rubina, J. T. Kim, A. V. Kel'in, V. Gevorgyan, J. Am. Chem. Soc. 2008,

130, 1440-1452. [7] A. S. Dudnik, Y. Xia, Y. Li, V. Gevorgyan, V. J. Am. Chem. Soc. 2010, 132, 7645-7655. [8] I. V. Seregin, V. Ryabova, V. Gevorgyan, J. Am. Chem. Soc. 2007, 129, 7742-7743. [9] C. Huang, V. Gevorgyan, J. Am. Chem. Soc. 2009, 131, 10844-10845. [10] A. S. Dudnik, V. Gevorgyan, Angew. Chem., Int. Ed. 2010, 49, 2096-2098. [11] N. Chernyak, A. S. Dudnik, C. Huang, V. Gevorgyan, J. Am. Chem. Soc. 2010, 132, 8270-8272.


PL3

STUDIES OF BIOMIMETIC METALLOPORPHYRIN MODELS

Roger Guilard

Université de Bourgogne, ICMUB (UMR 5260), 9 avenue Alain Savary, BP 47870, 21078 Dijon Cedex, FRANCE.

Our research effort in the field of bioinspired chemistry has spanned over three decades, with much of our effort being devoted to the synthesis and characterization of metalloporphyrin model compounds which can perform or mimic different biochemical, enzymatic and photochemical functions, the exact nature of which will vary with the properties of the specific tetrapyrrolic macrocycle being investigated. Several high points of our previous work as well as a discussion of our most recent investigations in the area will be given in the current talk which is divided into three main sections: I. Porphyrins with metal-carbon bonds which can lead to a better understanding of the

evolution of P 450 cytochrome derivatives; II. Pacman porphyrins which can selectively reduce dioxygen by a four electron mechanism

mimicking the cytochrome c oxydase, and III. Compounds which mimic the energy and electron transfer modules of Photosystems I and

II, our current interest. The above three topics have led to major collaborations over a number of years with Karl Kadish, James P. Collman and Pierre Harvey on the above topics I, II and III, respectively. Our advances in these areas were also made possible by the continuous support from numerous other collaborators as well as the important involvement of my own coworkers over the years, most notably Drs. Panayotis Cocolios, Alain Tabard, Jean-Michel Barbe, Claude Gros and Christine Stern. [1] Guilard, R.; Kadish, K. M., Chem. Rev. 1988, 88, 1121. [2] Collman, J. P.; Hutchison, J. E.; Lopez, M. A.; Tabard, A.; Guilard, R.; Seok, W. K.; Ibers, J. A.; L'Her, M.,

J. Am. Chem. Soc. 1992, 114, 9869. [3] Harvey, P. ; Stern, C. ; Guilard, R. ; « Bio-Inspired Molecular Devices of the Antennas in Photosynthetic

Bacteria », Handbook of Porphyrin Science, World Scientific, 2010, Vol. 11, in press. e-mail: [email protected]


PL4

SOME PROGRESS IN METAL-METAL BONDING

Rhett Kempe

Anorganische Chemie II, Universität Bayreuth, 95440 Bayreuth, Germany. Chemical bonding and in particular the nature of a chemical bond, the electronic structure and its reactivity, is of fundamental interest. Metal-metal bonding has received a lot of attention recently. In the talk it is focussed on two topics: polar metal-metal bonds and quintuple bonding. First, recent progress in synthesising polar metal-metal bonds namely unsupported bonds between rare earths (RE) and transition metals (TM) is discussed [1] with a special focus on using such bond formation methodologies to generate highly reactive albeit in solution and in the solid state stable RE-TM core-shell compounds [2]. Secondly, recent progress in quintuple bonding is discussed [3] with a special focus on synthesising compounds with ultra-short metal-metal bonds [4] and understanding quintuple bonds by their reactivity [4]. [1] M. V. Butovskii, O. L. Tok, F. R. Wagner and R. Kempe, Angew. Chem., Int. Ed., 2008, 47, 6469-6472. [2] M. V. Butovskii, Ch. Döring, V. Bezugly, F. R. Wagner, Y. Grin and R. Kempe, Nature Chem., 2010, 2, July

issue. [3] F. R. Wagner, A. Noor and R. Kempe, Nature Chem., 2009, 1, 529-536. [4] Noor, F. R. Wagner and R. Kempe, Angew. Chem. Int. Ed., 2008, 47, 7246-7249. [5] A. Noor, G. Glatz, R. Müller, M. Kaupp, S. Demeshko and R. Kempe, Nature Chem., 2009, 1, 322-325. e-mail: [email protected]


PL5

SYNCHRONIZED COOPERATION OF PD AND BRØNSTED ACID IN ADDITION OF SECONDARY PHOSPHINE OXIDES WITH ALKYNES

M. Tanaka

Chemical Resources Laboratory, Tokyo Institute of Technology 4259-R1-13 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan.

Some ten years ago an interesting regiochemical reversal induced by Ph2P(O)OH in Pd-catalyzed addition of Ph2P(O)H with terminal acetylenes was disclosed and [Ph2P(O)-Pd-OP(O)Ph2] species was proposed as key intermediate.1 During the course of addition-carbocyclization of α,ω-diynes with HP(O)Ph2,2 however, we have come across unexpected result that suggests the real active species is a zwitterionic palladium complex formed though hydrogen bonding with ligated P(O)Ph2 moiety with a Ph2P(O)OH (Scheme 1). Detailed study has shown (1) HP(O)Ph2 is activated by palladium center through oxidative addition, (2) resulting species interacts with Ph2P(O)OH through hydrogen bonding, forming an intermediate having PPh2(O-H-OP(O)Ph2), which is a sort of phosphine ligand and prone to dissociate to generate a vacant coordination site, and (3) then an alkyne occupies the site to undergo insertion. Thus, the whole process is carried by duo of palladium and Ph2P(O)OH. This type dual activation facilitates the catalysis more efficiently as compared with the regime without Ph2P(O)OH or other Brønsted acids and has been found to successfully work in addition of dialkylphosphine oxide to alkynes (Table 1). Brief summary of H-P bond addition reactions and recent progress are presented.

HOP

HP

HOP

R

P

RPd

L

PPh2

L

OPO HR

PdL

PPh2H

L

OP

O HI-1

PdL L

Markovnikov addition

P = P(O)Ph2

C6 H P(O)nBu2

C6

P

Pd(dba)2 (5 mol %)

+ toluene-d80.500 mmol0.500 mmol

yield (%)

15

H-P conv (%)

2680100

< 124

859

110 єC, 3 h

HOP(O)Ph2 (5%)

yes

no

yes

yes

ligand (P/Pd = 2)

dppben

dppben

PPh3PMePh2

86100dppeyes

Table 1. Addition of Bu2P(O)H with 1-octyneScheme 1

[1] L.-B. Han, R. Hua, M. Tanaka, Angew. Chem., Int. Ed. Engl. 1998, 37, 94. [2] J. Kanada, K.-i. Yamashita, S. K. Nune, M. Tanaka, M. Tetrahedron Lett. 2009, 50, 6196. Acknowledgements - e-mail: [email protected]


Section Lectures


S1

OXO- AND IMIDO-ALKOXIDE VANADIUM COMPLEXES AS PRECATALYTS FOR THE GUANYLATION OF AMINES

Antonio Antiñolo,a Fernando Carrillo-Hermosilla,a Javier Romero-Fernández,a Carlos

Alonso-Moreno,a Ana M. Rodríguez,a Isabel López-Solera,a and Antonio Oteroa

a Área de Química Inorgánica Facultad de Ciencias Químicas. Universidad de Castilla-La Mancha

Campus Universitario de Ciudad Real, 13071-CIUDAD REAL, SPAIN

The catalytic production of organic molecules of interest is one of the most important applications of the Inorganic Chemistry. In fact, the compounds containing nitrogen, such as amines, enamines, imines and derivatives are interesting compounds as bulk chemicals, or fine chemicals. At the present, there have been intensified the studies related to the synthesis and behaviour of transition metal complexes that contain in his structure one or more terminal imido ligands. These ligands could be implied in different catalytic processes or acting as stabilizer ligands of the active centre. In this communication, we present the synthesis and characterization of a family of oxoalkoxide derivatives of Vanadium (V), [VCl3-x(O)(OR)x] (x = 1, 2; R = Me, Et, Pr), as precursors of imidoalkoxide complexes, {VCl3-x[N(2,6-iPr2C6H3)](OR)x}2 (x = 1, 2; R = Me, Et, Pr). These complexes are very efficient catalysts in a guanylation process of aromatic amines, to the obtaining the corresponding N,N',N”-guanydines.

NH2

+ iPrN=C=NPriN

NH

NH

Acknowledgements - We gratefully acknowledge financial support from the MICINN of Spain (Grants No. CTQ2009-09214 and ORFEO PROJECT-CONSOLIDER INGENIO No. CSD2007-00006), and the Junta de Comunidades de Castilla-La Mancha (Grant No. PCI08-0032-0957). e-mail: [email protected]; [email protected]


S2

WHAT INTERATOMIC DISTANCES WE MAY CONSIDER AS A CHEMICAL BOND ?

M.Yu. Antipin

A.N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of

Sciences, 119991, Vavilov Str. 28, B-334, Moscow, RUSSIA.

Traditionally, a chemical bond between two atoms or groups of atoms is considered to exist in those cases when the distance between “bonded” atoms is close to the sum of their covalent radii. Quite many systems of these empirical values were described in literature, and for the same atom the covalent radius sometimes may differ by 0.01Å in different systems. More complicated situation about declaration the presence/absence of chemical bond arises when interatomic distance is larger than the sum of covalent radii, but is less than the sum of their van-der-Waals radii. This is the interval, where interatomic interactions are considered to be attractive and correspond to “additional” interactions, weak interactions, hydrogen bonds, “specific” interactions, etc. But in different systems of van-der-Waals radii (at least 8 such systems exists) the difference in radius for the same atom may be as large as 0.2 Å or even more. Therefore, it is very difficult sometimes to declare the presence or absence of chemical bond (attractive interaction) between two atoms on the basis of interatomic distances only, because result may depend, especially in case of weak interactions, on the choice of the system of van-der-Waals radii. In these cases the final conclusion will depend on chemical intuition and sense. So, interatomic distances in some cases (e.g. weak bonds) may not be considered as the only criteria of chemical bond, and other approaches must be developed. At present, physically most valid criteria of a chemical bond were suggested by R. Bader et al. in the frame of his theory “Atoms in Molecules” (AIM), and based on analysis of the topology of the full electron density distribution (ED) function, which may be obtained from accurate X-ray diffraction data or calculated from quantum chemistry. According to AIM, chemical bond (interatomic interaction) exists between two atoms, if there is a “bond path” and critical point (3,-1) between them in the relief of ED, and the density of the potential energy at critical point is negative. Note, that there is no interatomic distances in this definition, and all named values may be obtained from the accurate X-ray diffraction experiment. In the lecture, some examples of different molecular systems with large set of long and short interatomic distances, corresponding bonding/non-bonding situation, will be analysed in the frame of AIM theory. The systems studied include transition metal complexes and clusters, hypervalent derivatives of Si, Ge, Sn, cabroranes and metallocarboranes, strained organic molecules, molecular donor-acceptor complexes, and others.


S3

NEW MATERIALS FOR ORGANIC LIGHT EMITTING DIODES

Mikhail N. Bochkarev and Marina A. Katkova

G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA.

During 10 years in IOMC active search and investigation of new effective materials for OLEDs are currying out. Main efforts were concentrated on rare earth metals and their derivatives because low work function of these metals and same advantages which these metals have as emitters. In presentations achievements in the area of cathode materials and emitters are quoted. It was found that heterobimetallic composite Tm:Yb used as cathode in simple OLED of configuration ITO/TPD/Alq3/M (ITO- anode, TPD – hole-transport layer, Alq3 – emitting layer, M – cathode) provides best characteristics of a device as compared with tradition cathodes – Al, Ca:Al, Mg:Al. Four groups of rare earth complexes were synthesized and studied as emitters: (i) 8-oxyquinolates Lnq3 and their derivatives containing in 2-position of a ligand Me, CN and NH2 groups; (ii) imidodiphosphinate complexes Ln(pip)3; (iii) 2-mercaptobenzothiazolate complexes Ln(mbt)3 and (iv) phenolates containing in 2-position of the ligand 2-benzoimidazol-2-yl (Ln(non)3), 2-benzoxyazol-2-yl (Ln(oon)3) and 2-benzothiazol-2-yl (Ln(son)3) substituents. Highest efficiency and brightness were obtained for scandium complex Sc(oon)3. Most of the complexes were structurally characterized. For Lnq3, Ln(non)3, Ln(oon)3 and Ln(son)3 DFT calculation were performed. Some of these data have been confirmed by UPS measurements (Dr. S.E. Alexandrov, Dr. A.L. Shakhmin, St. Petersburg State Polytechnic University) which gave a chance to determine the energy level of HOMO and LUMO of the used compounds. The found value of HOMO and LUMO turned out in good agreement with electroluminesecent characteristics of the materials tested in modeling OLED devices of configuration ITO/TPD/Ln complex/Bath/Yb (Bath – electron-transporting layer). Design of effective electroluminescent complexes of rare earth metals are discussing. Acknowledgements - The work was supported in part by the Russian Foundation of Basic Research (Grants, 10-03-00190, 09-03-97016p). e-mail: [email protected]


S4

METALLOCOMPLEXES WITH CARBORANECHALCOGENOLATE LIGANDS

Vladimir I. Bregadze,a Sergey A. Glazun, a Olga B. Zhidkova, a Zoya A. Starikova, a Nisha P. Kushwah, b Manoj K. Pal, b Amey P. Wadawale, b Vimal K. Jain b,

Yuguang Lic, Qibai Jiangc, Yizhi Lic, Hong Yanc

a A.N.Nesmeyanov Institute of Organoelement Compounds, RAS, 28 Vavilov Str. 119991 Moscow, Russia, b Chemistry Divison, Bhabha Atomic Research Center, Mumbai, India,

cState Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Jiangsu 210093, China

The reactions of [M2Cl2(µ-Cl)2(PMe2Ph)2] with mercapto-o-carboranes in the presence of pyridine afforded mono-nuclear complexes 1-3. The treatment of [PdCl2(PEt3)2] with Ph-o-CB10H10CSH yielded trans-derivative 4 [1]. A variety of palladium and platinum complexes (5-7) have been isolated by the reactions of Ph-o-CB10H10CSeNa with [M2Cl2(µ-Cl)2(PR3)2] and [MCl2(PR3)2] [2].

PdPEt3S

Ph

Et3P

Ph

S

4

Se

Pd Pd

Cl

Se

Et3P

PEt3

Cl

Ph

Ph

5PR3=PMe2Ph 6 PMePh2 7

PtSe

Se

R3P

R3P

Ph

Ph

M=Pd, Pt; R=H, Ph

1 - 3

R

Me2PhPM

PyCl

S

CBH

A series of new compounds based on cobalt complex containing o-carborane thiolate ligand, CpCoS2C2B10H10, was prepared, such as CpCo(S2C2B10H9)(CH=CH-C(O)R) (8), [(CpCoS2C2B10H10)(CpCoSC2B10H11)(SC4H9)] (9), [(CpCo)2S2(S2C2B10H10)(SC2B10H10) (SC4H9)] (10), [(CpCo)2Co(SC4H9)6]+[Co(S2C2B10H10)2]- (11), [(CpCo)2Co(SC2B10H11) (SC4H9)5]+[Co(S2C2B10H10)2]- (12) [3-5]. [1] N.P. Kushwah, V.K. Jain, A. Wadawale, O.B. Zhidkova, Z.A. Starikova, V.I. Bregadze, J. Organomet. Chem., 2009, 694, 4146-4151. [2] M.K. Pal, V.K .Jain, N.P. Kushwah, A. Wadawale, S.A. Glazun, Z.A. Starikova, V.I .Bregadze, J. Organomet. Chem., 2010, in press. [3] Y. Li, Q. .Jiang, Y. Li, H. Yan, V.I. Bregadze, Inorg. Chem., 2010, 49, 4-6. [4] Y. Li, Q. Jiang, X. Zhang, Y. Li, H. Yan, V.I. Bregadze, Inorg. Chem., 2010, 49, 3911-3917. [5] Y. Li, Q. Jiang, X. Shen, Y. Li, H. Yan, V.I. Bregadze, Inorg. Chem., 2010, 49, DOI: 10.1021/ic100497h. Acknowledgements Authors are grateful to the Russian Foundation for Basic Researches (RFBR), Russian Academy of Sciences (RAS), National Science Foundation of China (NSFC) and Department of Science and Technology (DST), New Delhi, for financial support under ILTP project of RAS-DST No. B-5.22, RFBR-NSFC joint grant (09-03-92216 and 20911-20057) and RFBR-DST grant (10-03-92657-IND and RUSP-1005). e-mail: [email protected]


S5

SCADIUM TERMINAL IMIDO COMPLEXES: SYNTHESIS, STRUCTURES AND REACTIVITIES

Y. Chen, E. Lu and J. Chu

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry,

Chinese Academy of Sciences,354 Fenglin Road, Shanghai 200032, P.R.C. The terminal imido complexes of early-transition-metal, which containing the M=N double bond, have attracted intensive interesting in last two decades, due to their applications in the group transfer and catalysis procedures, as well as the unique structural properties [1]. Many examples of group 4 and 5 metal terminal imido complexes as well as the actinide ones have been reported. On the other hand, the synthesis of terminal imido complexes of rare-earth-metal (Sc, Y and lanthanide) is difficult [2]. The rare-earth-metal terminal imido species once formed easily assemble as the more stable bimetallics µ2-bridged imido complexes or multi-metallic imido clusters, or undergo reactions with solvents via C-H bond activation [3]. The increased Lewis acidity of the rare-earth-metal ion and high active Ln=NR double bond should led to interesting reactivities. The understanding of the nature of Ln=NR double bond is also of fundamental concern. Herein we present the use of multidentate nitrogen ligands to isolate and structurally characterize of the scadium terminal imido complexes as well as the reactivities of these complexes.

LSc=NR

L: multidentate nitrogen monanionic ligands

Reference: [1] (a) A. P. Duncan and R. G. Bergman, The Chemical Record., 2002, 2, 431; (b) L. H. Gade and P. Mountford, Coord. Chem. Rev., 2001, 216 – 217, 65; (c) D. J. Mindiola, Acc. Chem. Res., 2006, 39, 813. [2] G. R. Giesbrecht and J. C. Gordon, Dalton Trans., 2004, 2387. [3] (a) A. A. Trifonov, M. N. Bochkarev, H. Schumann and J. Loebel, Angew. Chem. Int. Ed. Engl., 1991, 30, 1149; (b) Z. W. Xie, S. W. Wang, Q. C. Yang and T. C. W. Mak, Organometallics, 1999, 18, 1578; (c) S. W. Wang, Q. C. Yang, T. C. W. Mak and Z. W. Xie, Organometallics, 1999, 18, 5511; (d) H. S. Chan, H. W. Li and Z. W. Xie, Chem. Commun., 2002, 652; (e) J. C. Gordon, G. R. Giesbrecht, D. L. Clark, P. J. Hay, D. W. Keogh, R. Poli, B. L. Scott and J. G. Watkin, Organometallics, 2002, 21, 4726; (f) D. J. Beetstra, A. Meetsma, B. Hessen and J. H. Teuben, Organometallics, 2003, 22, 4372; (g) A. G. Avent, P. B. Hitchcock, A. V. Khvostov, M. F. Lappert and A. V. Protchenko, Dalton Trans., 2004, 2272; (h) D. M. Cui, M. Nishiura and Z. M. Hou, Angew. Chem. Int. Ed., 2005, 44, 959; (i) C. L. Pan, W. Chen, S. Y. Song, H. J. Zhang and X. W. Li, Inorg. Chem., 2009, 48, 6344. Acknowledgements: This work was supported by the National Natural Science Foundation of China and Chinese Academy of Sciences. e-mail: [email protected]


S6

LIVING CATALYZED-CHAIN-GROWTH POLYMERIZATION AND BLOCK COPOLYMERIZATION OF ISOPRENE BY RARE-EARTH METAL ALLYL

PRECURSORS BEARING CGC LIGAND

D. Cuia, and Z. Jiana

aState Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, 130022, Renmin str, 5625, Changchun, CHINA.

Chain transfer polymerization has gathered an upsurge in research interests in the past decade, as which presents various advantages over single component catalyst polymerization such as atom economy, molecular weight control, and especially terminal functionlization of nonpolar polymers [1,2]. However, chain transfer is a dominant chain-termination pathway, giving oligomeric or low molecular weight polymers owing to the potential catalyst poisoning and deactivation. Therefore a process in which the transmetallation between the growing metal centers and the chain transfer agents majorly metal alkyl compounds, possessing a rapid and reversible character without termination reactions, sounds promising. This is the so called catalyzed-chain-growth (CCG) [3]. Herein we report the novel aminophenyl functionalized mono-cyclopentadienyl constrained-geometry-conformation lanthanide bis(allyl) precursors (C5Me4-C6H4-o-NMe2)Ln(η3-C3H5)2 (Ln = Y (1), Nd (2), Gd (3), Dy (4)). Complexes 1–4 with the activation of AliBu3 and [PhMe2NH][B(C6F5)4] displayed high cis-1,4 selectivity (98%) and excellent livingness for isoprene polymerization. Remarkably, in the presence of an excess amount of AliBu3, the unprecedented living CCG, a rapid and reversible transmetalation without termination, was achieved, indicating that each catalytic metal center produced more than one polymer chain with high molecular weight. [1] S. B. Amin and T. J. Marks, Angew. Chem., Int. Ed., 2008, 47, 2006-2025. [2] R. Kempe, Chem.–Eur. J., 2007, 13, 2764-2773. [3] A. Valente, P. Zinck, A. Mortreux and M. Visseaux, Macromol. Rapid Commun., 2009, 30, 528-531. Acknowledgements - This work is supported by The National Natural Science Foundation of China for project No. 20934006. The Ministry of Science and Technology of China for projects Nos. 2005CB623802; 2009AA03Z501. e-mail: [email protected], [email protected]


S7

POLYPHOSPHORYLPORPHYRINS – NEW BUILDING BLOCKS FOR SUPRAMOLECULAR NETWORKS FORMATION

Yu.G. Gorbunovaa,b, Yu. Yu. Enakievaa,b, E.V. Vinogradovaa, A. Bessmertnykhc, C. Sternc,

S.E. Nefedovb, Y. Rousselinc, A.Yu. Tsivadzea,b and R. Guilardc

aA.N. Frumkin Institute of General & Inorganic Chemistry of RAS, bN.S. Kurnakov Institute of General & Inorganic Chemistry of RAS, Leninskiy p.31, Moscow, 119991 RUSSIA, cUniversité de Bourgogne - ICMUB UMR CNRS 5260, 9 avenue Alain Savary - BP 47870, 21078 Dijon, FRANCE Metalloporphyrins are remarkable precursors in supramolecular chemistry and the rapid development of this chemistry led to many self-assembled networks1. The specific design of networks provides solid-state materials with unique electronic, optical, mechanical and catalytic properties. Polyphosphorylporphyrins represent a novel group of promising precursors with attractive binding properties, where P=O groups play a key role in the self-assembling process. Recently we have synthesized porphyrins possessing phosphoryl groups2 at the periphery of the macrocycle. Pd-catalysed coupling has been used to prepare meso-polyphosphorylporphyrins. The features of the networks formation using the synthesized meso-poly(diethoxyphosphoryl)porphyrins have been investigated in detail by means of X-ray crystallography, NMR, ESR and UV-Vis spectroscopy. It was shown that depending from the structure of porphyrin, the nature of transition metal and anion during complex formation as the ratio of reagents and solvent, 1D or 2D coordination polymers can be synthesized.

2D network We have been also involved in the synthesis of β-diethoxyphosphoryl substituted derivatives. These compounds are also promising precursors for molecular materials since β-functionalized porphyrins play a key role in the naturally occurring porphyrin self-assembling. It should be noted that β-phosphoryl porphyrins were unknown. Our first attempts have revealed that the transition metal-catalyzed phosphorylation of β-monobromo-substituted porphyrins is also a suitable method for the synthesis of such derivatives. [1] I. Beletskaya, V.S. Tyurin, A.Yu.Tsivadze, R.Guilard, C.Stern //Chem. Rev., 2009, 109, 1659. [2] Yu.Yu. Enakieva, A.G. Bessmertnykh, Yu.G. Gorbunova, C. Stern, Y. Rousselin, A.Yu. Tsivadze, and R. Guilard // Org. Lett., 2009, 11, 3842. Acknowledgements - This work was supported by ARCUS 2007 Burgundy-Russia project, Russian Foundation for Basic Research (grant#07-03-92212), the CNRS and Russian Academy of Sciences. e-mails: [email protected], [email protected]


S8

COMPLEXES WITH "SUPERPODAL LIGANDS" – REACTIVITY ENHANCEMENT, SURFACE MODIFICATION, AND

INFORMATION STORAGE

Andreas Grohmann

Technische Universität Berlin, Institut für Chemie, Straße des 17. Juni 135,

10623 Berlin, Germany; e-mail: [email protected]

Our work delineates some unusual reactivity patterns in iron complexes of highly

symmetrical polyamines/polyimines L and pyridine-derived polyphosphanes L’. The

complexes have a “labile” sixth coordination site, thereby creating a platform for reactivity

studies of small monodentate ligands.[1]

The modification of the ligands with respect to variations in the donor set and—in the

case of FeN6 complexes—spin state switching will also be discussed. With a view to creating

spin-switchable units on surfaces, we are investigating the self-assembly of iron(II)

complexes containing pairs of planar terdentate nitrogen ligands on highly oriented pyrolytic

graphite (HOPG).[2]

[1] A. Grohmann, Dalton Trans. 2010, 39, 1432 – 1440.

[2] M. S.Alam, M. Stocker, K. Gieb, P. Müller, M. Haryono, K. Student, A. Grohmann, Angew. Chem.

2010, 122, 1178 – 1182; Angew. Chem. Int. Ed. 2010, 49, 1159 – 1163.


S9

CHEMISTRY OF PYRIDINE-2-SELENOLATE AND -TELLUROLATE COMPLEXES OF PLATINUM GROUP METALS AND MAIN GROUP

ELEMENTS

Vimal K. Jaina, G. Kedarnath, Rohit Singh Chauhan, Amey P. Wadawale and Rakesh K. Sharma

aChemistry Division, Bhabha Atomic Research Centre, Mumbai-400 085, INDIA

.

Pyridine-2-chalcogenolate ligands (I) represents an interesting family of hemilabile ligands. The chemistry of 2-oxo and 2-thio pyridine ligands has been extensively explored, while the coordination chemistry of 2-selenopyidines has been investigated only recently by others and us. In contrast, chemistry of 2-telluropyridines is still in infancy.

This presentation aims to discuss our results on pyridine-2-selenolate and-tellurolate

complexes of platinum group metals and main group elements1-3. Reactions of [Pt(PPh3)4] with dipyridylditellurides yield, in addition to simple oxidative addition product, [Pt(Tepy)2(PPh3)2], a serendipitous complex, [Pt(Te)(Tepy)2)(PPh3)] containing tellurium(0) as a ligand. Reactions of metal halides of main group elements with the NaEpy (E = Se or Te) afforded several selenolate and tellurolate complexes including [Cd(Tepy)2(tmeda)], [Hg(Tepy)2], [M(Sepy)3] (M = Sb or Bi), [In(Sepy)3], [Cu(Epy)]4 (E = Se and Te). The main group metal complexes have been used as molecular precursors for the preparation of metal chalcogenide nanostructures and deposition of thin films.

[1] G. Kedarnath, V.K. Jain, A. Wadawale and G. K. Dey, Dalton Trans., 2009, 8378 [2] R. S. Chauhan, G. Kedarnath, A. Wadawale, A. Muñoz-Castro, R. Arratia-Perez, V. K. Jain and W. Kaim,

Inorg. Chem., 2010, 49, 4175 [3] R. K. Sharma, G. Kedarnath, V. K. Jain, A. Wadawale, M. Nalliath, C. G. S. Pillai and B. Vishwanadh,

(unpublished results) e-mail: [email protected];


S10

LANTHANOID AND GROUP 2 COMPLEXES INVOLVING ARYLOXIDE LIGANDS OF MODERATE STERIC BULK

Glen B. Deacon, a Peter C. Junk,a Graeme J. Moxeya and Josh P. Townleya

aSchool of Chemistry, Monash University, Clayton, Victoria, 3800, AUSTRALIA

Traditionally, ligands of large steric bulk have been used to stabilize and isolate metal complexes and to control the coordination environment of the metal, while inhibiting polymerization of the compounds, in metal-organic chemistry. Phenolate ligands with sterically demanding groups on the 2,6-positions (e.g. tBu, Ph) have been used in this regard to synthesise lanthanoid aryloxides with low coordination numbers and compounds of high structural novelty.1 Recently we have been interested in phenolate ligands of modest steric2 bulk to moderate the degree of de-aggregation in attempts to form polynuclear lanthanoid and group 2 cage complexes. To do this, we have used the 2,6-dimethylphenolate, 2,4,6-trimethylphenolate and 2,4-di-tert-butyl phenolate in metal based reactions (equation 1) to study these systems. In this presentation, the results obtained from this chemistry will be discussed.

M + Hg(C6F5)2 + 2LH -------> ML2 + 2C6F5H + Hg↓ (1a) (M = Group 2 or lanthanoid metal)

2Ln + 3Hg(C6F5)2 + 6LH -------> 2LnL3 + 6C6F5H + 3Hg↓ (1b)

2Ln + 6LH --------> 2LnL3 + 3H2 (1c)

Figure 1: Structure of [Ba5(Omes)5(OMe)5(dme)4]·dme

Reference 1. Deacon,G.B.; Forsyth, C.M.; Junk, P.C.; Skelton, B.W.; White, A.H. Chem. Euro. J., 1999, 5, 1452-59; Deacon, G.B.; Junk, P.C.; GJ Moxey, G.J.; K Ruhlandt-Senge, 2. K.; C. St. Prix, C.; FelisaZuniga, M. Chem. Eur. J. 2009, 15, 5503-5519; Deacon, G.B.; Junk, P.C.; Moxey, G.J.; Guino-o, M.; Ruhlandt-Senge, K. Dalton Trans., 2009, 4878-4887; Deacon, G.B.; Junk, P.C.; Moxey, G.J. Chem. Asian J., 2009, 4, 1717-1728; Deacon, G.B.; Junk, P.C.; Moxey, G.J. Dalton Trans.., 2010, submitted; Clark, L.; Deacon, G.B.; Forsyth, C.M.; Junk, P.C.; Mountford, P.; Townley, J.P. Dalton Trans., 2010, submitted. e-mail: [email protected]


S11

COMPOSITION, STRUCTURE AND NUCLEARITY OF 3d METALS HOMO- AND HETEROLIGAND CARBOXYLATES AS FACTORS OF DIOXYGEN AND

HYDROPEROXIDES ACTIVATION

G.L. Kamalov

A.V. Bogatsky Physico-Chemical Institute of National Academy of Sciences of Ukraine, Department of Catalysis; 65080, Lustdorfskaya Doroga, 86, Odessa, UKRAINE.

On the examples of dibenzyl ether (DBE, the waste product of some makings) and cyclohexene (CH) liquid-phase oxidation by air oxygen (1 and 2) and by hydrogen peroxide (3 and 4, respectively), decomposition of hydroperoxides НР (5), СННР (6) and Н2О2 (7) in the presence

PhCH2OCH2Ph PhCH(OOH)OCH2PhO2

O22 PhCHO 2 PhCOOH- H2O

DBE HP

BAld BAc

PhCOOCH2PhO2

O2

BAldPhCHO

BB

(1)

OOH OH O

OO2 -H2O

CH-ol CH-on CHE

+ +

CH CHHP

CH(2)

of homo- and heterometallic (Cr, Fe, Mn, Сo, Ni, Cu, VO, Pd) polynuclear carboxylates (pivalates, benzoates, acetates – more than 100 complexes in total, with nuclearity from 2 to 12), the influence of the metals’ nature and their oxidation level, the character of bridging and terminal ligands and also the nuclearity of the studied complexes on the rate and selectivity of the specified reactions are discussed. Possible mechanisms of the dioxygen, substrates and intermediates activation and the peculiarities of formed catalytic systems caused by structure and composition of initial complexes, and also character of substrates and reaction products are considered. The structures of DBE, BAld and BAc complexes (XRSA), singled out in the conditions of the reaction 1 catalysis by Cu, Fe, Co and Pd pivalates are discussed. Possible mechanisms of these complexes formation are offered. The assumption about the promotion of catalytic reactions 5 and 6 by corresponding alcohols is come out. The catalysts demonstrated high selectivity in reactions 1 and 2 are revealed. That allows to realize coupled oxidation of СН to the CHE or СН-on. In the case of Co and Cu complexes the dependence of reaction 7 rate from the hydrogen peroxide and the catalyst (Cat) concentrations has extreme character. That specifies in essential passivation of the initial metal-complex at certain ratio Н2О2:Cat. It is revealed that selectivity on products of reaction 3 are approximated by two- or three-parameter equations, arguments of which are rates of reaction 7 in water or in aqueous emulsion of DBE. Close connections of reaction 6 rate with the rates of reaction 7 and СННР formation in reaction 2 in the presence of Co-complexes are found out. The assumption is come out that formation and decomposition of О-О bonds in these reactions occurs on the same «catalytic centers». Acknowledgements - This work was executed in frame of the Projects of INTAS (00-0172 and 03-51-4532), Ukrainian Fund of Basic Researches (F7/463-2001) and Joint Competition «National Academy of Sciences of Ukraine –Russian Fund of Basic Researches» (№ 32-08). e-mail: [email protected]; [email protected]


S12

NOVEL COMPLEXES OF CYCLIC AND MACROCYCLIC

AMINOMETHYLPHOSPHINES WITH TRANSITION METALS

A. Karasika, E. Musinaa, A. Baluevaa, S. Ignat’evaa, K. Kanunnikova, I. Strel’nika, R. Naumova, O. Naumovaa, E. Hey-Hawkinsb, O. Sinyashina.

a A. E. Arbuzov Institute of Organic and Physical Chemistry of Kazan Scientific Center of

Russian Academy of Sciences, 420088, Arbuzov str, 8, Kazan, RUSSIA. b Institut für Anorganische Chemie der Universität Leipzig, Johannisallee 29, 04103 Leipzig,

GERMANY.

Various types of P,N-containing heterocycles and macrocycles [1] form a wide variety of transition metal complexes. For example meso-1,3,6-azadiphosphacycloheptanes 1 [2] form chelate neutral 2 and charged complexes 3 much faster than rac-heterocycles 1 form

oligomeric complexes; that phenomenon was used for the separation of stereoisomers. The new 14-membered corand 4 formed by the condensation of

1,2-bis(phenylphosphino)ethane, formaldehyde and isopropylamine gives mononuclear macrocyclic complex 5 with platinum (II) dichloride, whereas 16-membered corands form mixtures of polynuclear macrocyclic comple-xes (e.g. 6) and metal complexes of the 1-aza-3,7-diphospha-cyclooctanes (7, 8).

28-, 36- and 38-membered P,N-containing cyclophanes form stable binuclear bis-P,P-chelate complexes. The metal ions of the P-menthyl substituted complexes 9 being located outside the the cavity according to X-ray data. So these different types of P,N-containing ligands may be considered as a potential basis for the catalytic and molecular recognition systems. [1] A. A. Karasik, A.S. Balueva, O. G. Sinyashin. C. R. Chimie, 2010, in press, doi: 10.1016/j.crci.2010.04.006 [2] A. A. Karasik, A.S. Balueva, E.I. Moussina et al. Heteroatom Chem, 2008, 19, 125-132 Acknowledgements: This work is supported by RFBR (09-03-12264-ofi-m, 10-03-00380-а, 09-03-91338-DFG_a) and by Federal Agency of Science and Innovations (state contract 02.740.11.0633) e-mail: [email protected]

R'

HR

Ph

Ph

NP P+ +R

H

Ph

PhN PP

1-meso

R'

1-rac1 1-rac2

R'

HR

Ph

PhNP P

** *

R'

RH

Ph

PhN PP

M

ClCl

R'

RH

Ph

PhN PP

M

RH

Ph

Ph NPP

R'

[M] 1/2 [M]

[M]

oligomers

R = Ph, C6H4OMe-p

R' = Me, Et[M] = MCl2(COD), MCl2

M = Pt, Pd, Ni

2+

2 Cl-2

3

CH3

CH3Ph

PhCH3

CH3

PhPh

NP

P

N

P

P

CH3

CH3

Ph

PhCH3

CH3

PhPh

NP

P

N

P

PPt

2+

2 Cl-

PtCl2(COD)

4 5

PH

PHPh

Ph

2 CH2O,i-PrNH2

P

P N

N XX

P

PN

NXX

Ar

Ar

M

M

R

R

R

R

ClCl

ClCl

XAr

XO O

M = Pt; Pd= , R = Ment

PP

N

Ni

Mes

Mes

Br Br

Ph8

;

976

PP

N

Cu

Mes

Mes

I

I

Ph

PP

N

Cu

Mes

Mes

Ph

P

P

N

N

P

P

Ar

Ar

Ar

Ar

M M

Ar'

Ar'M = CuI Ar = Ph, Mes;

Ar' = Ph, Py


S13

LUMINESCENT METALLOCOMPLEXES OF FUNCTIONALIZED PYRIDINES: FROM LIGAND DESIGN TOWARDS SPECIAL PROPERTIES

D.N. Kozhevnikova,b, D.S. Kopchuk,b M.Z. Shafikovb and A.M. Prokhorovb

aI. Postovsky Institute of Organic Synthesis of Ural Branch of Russian Academy of Sciences,

S. Kovalevskoy 20, Ekaterinburg, 620990,RUSSIA bUral Federal University, Mira 19, Ekaterinburg, 620002, RUSSIA

Design of organic ligands is one of the most powerful tools for tunning properties of transition metal complexes. Target changes in the ligand structure could give or improve accessary properties: solubility, self-organizing, liquid crystallinity etc., in addition to main desired property: luminescence, catalysis, recognition etc. We discuss methods for synthesis of substituted mono-, bi- and terpyridines which allow wide modification of these well-known ligands. Any synthesis is based on transformation of 1,2,4-triazine precursors towards desired pyridines through aza Diels–Alder reaction. The main advantage of such approach is wide diversity of substituents, which control different properties of target zinc(II), platinum(II), iridium(III), europium(III) complexes. In particular, liquid crystal properties can be added to luminescence of cyclometallated Pt(II) or Ir(III) complexes of 2-arylpyridines 1 by introduction of alkyl and cycloalkyl substituents.

5’-Aryl-2,2’-bipyridine-6-carboxylates were found to give neutral lanthanide(III) complexes 2. The cyclopentane ring in one of the pyridine rings increase dramatically solubility of the complexes, e.g. Eu(III), in organic solvents. At the same time, the aromatic substituents play the key role in intra- and intercomplex π,π-interactions, which affect luminescent properties. In particular, unusual for europium(III) complexes excimer luminescence was registered. Formation of excimers was proved by measurements of luminescence spectra of DCM solutions of the complexes at different concentrations. Introduction of iminoacetate moieties gave ligands for luminescent europium complexes 3 – potential biolabels. Acknowledgements. This work was supported by Russian Foundation For Basic Researches e-mail: [email protected]


S14

ORGANOMETALLIC CLUSTERS WITH PARTLY MULTIPLE BONDS BETWEEN TRANSITION AND NONTRANSITION ELEMENTS

A.A.Pasynskii

N. S. Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of

Sciences, 119991, Leninsky prosp., 31, Moscow, RUSSIA. The role of vacant and half-occupied orbitals in electron-deficient complexes is discussed at the formation of partly multiple strictly shortened bonds between transision (M) and nontransition (E) elements with participation of lone pairs of the latest. These bond coud be regulated at the addition of the metalcontaining fragments to such lone pairs. It influences on spin-spin exchange interactions via bridge ligands. It is shown that multiple М-E bonds ( М = Cr, Mn, Re; Э= S, Se, Te) are coordinated with Pt-containing fragments as olefins giving new types of mixed-metal clusters. The same complexes could be prepared by Pt-transmetallation of СрMn(СО)2 or Fe(CO)3 containing clusters [1]. The formally ordinary М-E bond’s distances are strictly shortened if E are nontransition elements of III-V periods where the antibonding orbitals of E-X could participate in additive М-E interactions (with E-X bond lengths elongation) or the vacant d-orbitals of E ared used for additive М-E interactions (without E-X bond lengths elongation). It is important that the elements M and E which participate in partly multiple M-E bonds retain at the cluster’s thermolyses but in the case of carbonyl-chalcogenide or carbonyl-pnicogenide clusters the presence of excess of metal atoms in respect to chalcogen atoms results electronecompensated CO group disruption with metal carbides and -oxides formation. It gives the opportunity to regulate the composition of inorganic products of cluster pyrolises particulary at the preparation of Pt-containing mixed-metal electrocatalysts for fuel cells. In stannylated clusters the formally ordinary М-Sn bonds are strongly shortened and in the presence of tin-chalcogen bonds the latter retain at W(CO)5 addition to S atom but the Sn-Se bonds are disrupted in this situation with pure W-Se-containing complexes formation. The strong shortening of Pt-Sn and Ru-Sn bond lengths takes place even at the М/Sn ratio 1:5 or 1:3 respectively. The positive influence of the M-Sn bonding on catalytical reactions of olefine metatheses or alcohol oxidation is discussed. Finally the new type of Te-containing complexes are discussed where the presence of very short M-Te bonds (even at М:Те ratio 1:3) is combined with additive interaction between halogen atoms at M with Te atoms at M. Acknowledgements: this work was financially supported by RFBR (grant № 09-03-00961). [1]. A.A. Pasynskii, I. V. Skabitsky, Yu. V. Torubaev, S.S.Shapovalov// J.Organomet.Chem. 2009. V.694. N21.P. 3373-3375. e-mail: [email protected]


S15

INTERPLAY OF ASSOCIATIVE AND DISSOCIATIVE ONE-ELECTRON PROCESSES IN ORGANOMETALLIC CHEMISTRY: ACCESS TO PRECISION

POLYMERS WITH CONTROLLED FUNCTIONALITY

Rinaldo Poli a, Antoine Debuigneb and Christophe Detrembleurb

a Laboratoire de Chimie de Coordination, 205, route de Narbonne, F-31077 Toulouse, France and Institut Universitaire de France, 103, bd Saint-Michel, 75005 Paris, FRANCE.

b Center for Education and Research on Macromolecules (CERM), University of Liège, Sart-Tilman, B6, 4000 Liège, BELGIUM

Transition metal complexes may be implicated in controlled radical polymerization, a booming area for the development of high added-value polymer materials. They may be catalysts in “atom transfer radical polymerization” (ATRP), trapping agents in “organometallic radical polymerization” (OMRP), catalysts for chain transfer to monomer (CCT), and transfer agents for “degenerative transfer polymerization” (DTP).1 This lecture will focus on the interplay of OMRP and DTP for the controlled polymerization of a difficult monomer, vinyl acetate (VAc), for which ATRP has not provided a satisfactory level of control. Understanding the key role of solvent coordination (Scheme 1) has allowed us to develop the precision polymerization of this monomer2 and the synthesis of well defined block-copolymers with a PVAc block,3 as well as an efficient diene-induced radical coupling process leading to mid-chain functionalized macromolecules.4

References [1] Poli, R. Angew. Chem., Int. Ed. Engl. 2006, 45, 5058–5070. [2] (a) S. Maria, H. Kaneyoshi, K. Matyjaszewski and R. Poli, Chem. Eur. J. 2007, 13, 2480-2492. (b) Debuigne,

A.; Poli, R.; Jérôme, R.; Jérôme, C.; Detrembleur, C., ACS Symp. Ser. 2009, 1024, 131-148. [3] A. Debuigne, C. Michaux, C. Jérôme, R. Jérôme, R. Poli and C. Detrembleur, Chem. Eur. J. 2008, 14, 7623-

7637. [4] (a) Debuigne, A.; Poli, R.; Winter, J. D.; Laurent, P.; Gerbaux, P.; Dubois, P.; Jean-Paul, W.; Jérôme, C.;

Detrembleur, C., Chem. Eur. J. 2010, 16, 1799-1811. (b) A. Debuigne, R. Poli, J. D. Winter, P. Laurent, P. Gerbaux, J.-P. Wathelet, C. Jérôme and C. Detrembleur, Macromolecules 2010, 43, 2801-2813.

Acknowledgements – We are grateful to the CNRS and to the ANR (Grant No. NT05–2 42140) for funding and to CICT for franting free computational time. e-mail: [email protected]

+ Co(acac)2PVAcn Co(acac)2-PVAcn•V-70

kdR0

• VAc+ Co(acac)2PVAcn Co(acac)2-PVAcn

•V-70kd

R0• VAc

kpVAc

Co(acac)2-PVAcmPVAcm

•

PVAcn•

DTP

V-70kd

R0•

VAc

kpVAc

Co(acac)2-PVAcmPVAcm

•

PVAcn•

DTP

V-70kd

R0•

VAc

Co(acac)2(L)2-L

+L

+L-L +L-Lslow(CoIII inert)fast(CoII labile)

OMRP

Co(acac)2(L) Co(acac)2(L)-PVAcn

PVAcn•

+

kp VAc

Co(acac)2(L)2-L

+LCo(acac)2(L)2

-L

+L


OMRP


PVAcn•

+

kp VAc


OMRP


PVAcn•

+

kp VAc

PVAcn•PVAcn•

Scheme 1: OMRP/DTP interplay in the controlled radical polymerization of VAc


S16

ORGANIC LIGHT-EMITTING DIODES – THE CURRENT STATE OF INVESTIGATIONS AND DEVELOPMENTS

V.F. Razumov

Institute of Problems of Chemical Physics of Russian Academy of Sciences, 142432, acad. Semenov av., 1, Chernogolovka, Moscow region, RUSSIA.

Organic light-emitting diodes (OLEDs) are double charge injection devices, requiring the simultaneous supply of both electrons and holes to the electroluminescent (EL) material sandwiched between two electrodes. The simplest OLED configuration, where an organic emitter layer is sandwiched between a transparent anode and a metallic cathode, gives very poor efficiency. The use of two or more different materials, e.g. electron- or hole- transport materials (ETM or HTM) permits to improve the efficiency. Among these materials the special place is occupied by organic heterocyclic compositions and metallocomplexes. One of the first in this row was tris(8-hydroxyquinoline)aluminum (Alq3), presented in 1987 by Tang as an emitter and electron-transport material. Today derivatives of diarylsubstituted 1,3,4- oxadiazoles are widely used. They are the basis both of electron-transport and luminescent layers. More effective luminescent and electron-transport materials than oxadiazoles are triarylsubstituted 1,2,4-triazoles. Recently the great attention is given to condensed pyrasolochinolines which can be used both in the form of individual layers and dopants. Other large class of electron transport materials is metallocomplexes with aluminium, zinc, iridium and platinum as metals. Derivatives of 8-gidroksihinolin, 2-gidroksifenil-2-benzazols and some others are used as ligands. Chinolinat aluminium possesses good electron transport properties, a high photoluminescence and quite good electrophysical characteristics. Zinc complexes of benzoxazole, benzothiazole and benzimidazole derivatives also are rather perspective electron transport luminescent materials. They concede Alq/3 on brightness, but surpass this "reference" complex by one order in mobility of negative charges. Recently the great interest is given to use of colloidal semiconductor quantum dots (QDs). Incorporating QDs into OLED structures as emitting materials is connected with their specific properties: i)high quantum yield of photoluminescence which is perspective for obtaining high-luminance LEDs; ii)narrow spectral distribution of QD luminescence bands which is important for display applications; iii)possibility to obtain QD luminescence in any visible spectral region (blue, green, red) which is important for full-color displays and for white light sources. In this report the review of modern achievements of use of organic heterocyclic and metallocomplex compounds in OLEDs is presented.

e-mail: [email protected]


S17

RELATIONSHIPS OF KINETIC AND THERMODYNAMIC PARAMETERS OF DIHYDROGEN BONDING AND PROTON TRANSFER TO TRANSITION METAL

HYDRIDES

E.S. Shubina, N.V. Belkova and L.M. Epstein

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 119991, Vavilov Street 28, Moscow, RUSSIA

. Рroton transfer involving transition metal hydrides and/or heterolytic splitting of dihydrogen are important steps in many catalytic processes, including ionic hydrogenation and reduction of H+ to H2. Protonation of metal hydride complexes is generally recognized as the most common method of [M(η2-H2)] preparation.[1] Detailed studies of the mechanism of proton transfer to transition metal hydrides have firmly shown that, in spite of its apparent simplicity, the process involves several steps and proceeds via various hydrogen bonded intermediates of molecular or ionic type (Scheme 1).[2-4] M-H + H-A M-H···H-A [M(η2-H2)]+···A- [M(η2-H2)]+ // A-

molecularcomplex

hydrogen bonded ion pair

solvent separated ion pair

M-H + H-A M-H···H-A [M(η2-H2)]+···A- [M(η2-H2)]+ // A-M-H + H-A M-H···H-A [M(η2-H2)]+···A- [M(η2-H2)]+ // A-

molecularcomplex

hydrogen bonded ion pair

solvent separated ion pair

Scheme 1. The analysis of the recent results on proton transfer to transition metal hydrides will be presented. The balance of the transition metal atom electron richness and of ligand electronic and steric properties determines the proton transfer pathway and structure of the intermediates and of the reaction products. The relationships of kinetic and thermodynamic parameters of dihydrogen bonding, MH···HA, proton transfer, yielding [M(η2-H2)] species, and subsequent steps such as[M(η2-H2)] to [M(H)2] isomerization or H2 evolution will be analysed.

Hydrogen bond strength, hydride ligands proton accepting ability will be shown to correlate with the kinetics and thermodynamics of the proton transfer. The experimental data backed up by the theoretical results allow discussing the possible types of potential energy profiles. Factors such as proton donor and solvent nature, cooperative effect, temperature etc. will be shown to determine stability of the species involved. The knowledge acquired gives wide scope for tuning the reactivity of hydride and dihydrogen complexes and for governing the reaction pathway.

[1] G. J. Kubas, Chem. Rev. 2007, 107, 4152-4205 [2] N. V. Belkova, E. S. Shubina, L. M. Epstein, Acc. Chem. Res. 2005, 38, 624-631. [3] N. V. Belkova, L. M. Epstein, E. S. Shubina, ARKIVOC 2008, iv, 120-138. [4] M. Besora, A. Lledos, F. Maseras, Chem. Soc. Rev. 2009, 38, 957-966 Acknowledgements - The work was supported by the Division of Chemistry and Material Science of RAS and RFBR (08-03-00464) . e-mail: [email protected]


S18

YTTERBIUM COMPLEXES WITH REDOX-ACTIVE DIIMINE LIGANDS: FAIRLY RICH CHEMISTRY AND PROMISING PRECURSORS FOR NEW MATERIALS

A. Trifonov, B. Shestakov

G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences,

603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA.

Combination of diimine ligands possessing diverse coordination and redox properties with lanthanide metals which have two stable oxidation states (especially with ytterbium) have resulted in development of rich and intriguing organometallic chemistry. The reductive reactivity of ytterbocenes towards α,α’-diimines proved to be sterically and electronically tunable; depending on the extent of encumbering of the metal atom coordination sphere and the nature of metal-ligand bonding these reactions can occur with metal atom oxidation, C-C bond formation, C-H bond activation, C=N bond hydrogenation. Moreover, manipulation of steric crowding of the ytterbium coordination sphere allows to switch the reductive capacity of ytterbocenes in their reactions with α,α’-diimines from one- to two-electron reduction.

An expansion of ytterbocene reductive chemistry due to employment of α,α’-diimines reveals new for this field phenomena: solvent mediated redox tranformations and temperature induced redox isomery.1 All these phenomena will be discussed. New types of reactions of ytterbocenes with diazabutadienes, iminopyridines, 7,7,8,8-tetracyanoquinodimethane and 1,2,4,5-tetracyanobenzene as well as novel types of ytterbium complexes with diimines will be reported. [1] Trifonov, A. A. Eur. J. Inorg. Chem. 2007, 3151. Acknowledgements - This work was supported by the Russian Foundation for Basic Research (Grant N 08-03-00391-а), Program of the Presidium of the Russian Academy of Science (RAS), and RAS Chemistry and Material Science Division. e-mail: [email protected]


S19

CORE-SHELL QUANTUM DOTS AND ORGANIC LIGHT EMITTING DEVICES

A.G. Vitukhnovsky, S.A. Shirokov, A.V. Ovchinnikov and S.A. Ambrozevich

P.N. Lebedev Physics Institute RAS, Leninsky ave. 53, 119991 Moscow, RUSSIA. The ideas of fabrication of light emitting devices based on organic matrices doped with inorganic semiconductor quantum dots (QDs) are considered as challenging. The quantum dots can be used as an active layer in organic light emitting diodes (OLEDs). New hybrid OLEDs with embedded quantum dots (QD-OLEDs) have improved life times, high color rendering index and low fabrication cost. Another one branch of organic electronics which involves quantum dots is a development of organic field effect transistors (OFETs) which under certain conditions can also behave as a light emitter devices – organic light emitting transistors (OLETs) [1]. The key unit of QD OLED is a two-layer (core - shell) nanocrystal (QD) covered with an organic layer preventing the multiple nanocrystal aggregation. In the present work we review the electronic properties of semiconductor QD taking into consideration the hybrid band structure of core and shell semiconductors. Type I and type II structures are discussed. It is shown that the type I quantum dots have larger quantum efficiency that the quantum dots of type II. The nanocrystals are investigated using luminescence spectroscopy, luminescence decay with picosecond and femtosecond time resolution, and by tracing the blinking fluorescence of a single nanocrystal. The differences between the light emitting properties of spherical and tetrapod-shaped nanocrystals are revealed by means of photoluminescence decay experiment. The tetrapod nanocrystal photoluminescence decay has a non-exponential shape due to the limitation of the radiative recombination rate by the tunneling of the electron over the potential barrier in the junction point of the tetrapod core [2]. The possibilities to implement OLEDs/OFETs with top-emitting and bottom-emitting geometries are reported. Several problems of increasing the overall performance of the organic devices (e.g. on-off current ratio increase in an OFET) are discussed.

[1] R.Capelli, S.Toffanin,G.Generali et al., Nature Matrials, 2010, 9, 496. [2] A.G. Vitukhnovsky et al,, Phys. Lett. A, 2009, 373, 2287.

Acknowledgements - Authors acknowledge the Russian Foundation for Basic Research, project 09-02-00546-a. e-mail: [email protected]


Oral Presentations


O1

NORBORNENE-BASED METAL-CONTAINING POLYMERS. SYNTHESIS AND LUMINESCENT PROPERTIES

L. N. Bochkarev a

aG. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences,

603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Novel functionalized norbornene monomers were synthesized: Ring opening metathesis polymerization of functionalized norbornene monomers was employed for preparation of lanthanide- and platinum-containing polymers of the types: Photo- and electroluminescent properties of the synthesized metal-containing polymers will be discussed. Acknowledgements - this work was supported by the Russion Foundatin for Basic Research (Project № 08-03-00436) e-mail: [email protected]

C=OO

NN N

NN

CH3 O

O

O=C

N

C=OO

NN N

Eu

S

O O

CF3 3

C=OO

NN N

Tb

NN

CH3

O O

3

OOLn

(CH2)5

OOH N

N

2

n

Ln = Tb, Eu

OO

(CH2)5

OOH N

N

2

n

OO

(CH2)5

OOH N

N

2

m

Tb Eu

(CH2)5

x

N

n : m : x = 1 : 1: 10

CH2

O O

Pt

n

(H2C)5N

m

m : n = 10 : 1

N

n

(H2C)5N

m

m : n = 10 : 1

NN

CH3 O

O

NPt

C=OO

NN N

Eu

S

O OCF3 3

n

N

m

m : n = 5 : 1

O=C

C=OO

NN N

Tb

n

O=C

N

m

m : n = 5 : 1

NN

CH3

O O

3


O2

NEW 2,2’-BIPYRIDINE-BASED POLYDENTATE LIGANDS FOR NUCLEAR WASTES SEPARATION

N. Borisovaa, E. Eroshkinaa, V. Gerasimchuka, K. Lisenkob, V. Babainc, M. Reshetovaa and

Yu. Ustynyuka

aMoscow State University Chemistry Department, 119991, Leninskie Gory, 1/3, Moscow, RUSSIA.

bA.N. Nesmeyanov Institute of Organoelement Compounds, 119991, Vavilova st., 28, Moscow, RUSSIA.

cV.G. Khlopin Radium Institute, 194021, 2-nd Murinskiy Prospect, 28, S.-Petersburg, RUSSIA.

Separation of minor actinides (particularly americium and curium) from rare earth elements is very important step of nuclear spent fuel reprocessing strategies. The mail goal of this investigation was synthesis and investigation of extraction properties of the novel compounds based on 2,2’-bipyridyl unit. New ligands for complexing of the posttransition metals were developed, synthesized and characterized. We synthesized a number of amides (1) bearing different substituents on amide moiety as well as at the positions 4 and 4’ of pyridine rings. The reactions of the amides 1 and lanthanides were studied in details by spectrophotometry and NMR. Binding constants for all of the lanthanide ions with amides of 2,2’-bipyridyl-6,6’-dicarboxylic acid were found to lie within the range of 4


O3

MICRO -RAMAN SPECTROSCOPY AS AN INDISPENSABLE METHOD OF IDENTIFICATION AND STRUCTURAL INVESTIGATION OF VARIOUS

sp2-CARBON MATERIALS

S.S. Bukalov

Scientific and Technical Center on Raman Spectroscopy, A.N. Nesmeyanov Institute of Organoelement Compounds,

The Russian Academy of Sciences, Vaviliva str. 28, Moscow119991 RUSSIA.

Various sp2-carbon materials and composites on their basis are widely studied in

modern high technologies. In view of this, the methods for their distinguishing and structural

studies are badly needed. These materials are made of graphene layers of different geometry

packed as bundles or crystallites, whose characteristics and sizes determine their macroscopic

properties. Micro-Raman spectroscopy on its modern level is one of the most convenient,

adequate, nondestructive methods of such kind, because each type of sp2-carbon material

exhibits its own diagnostic Raman spectrum of the first and second order, that is characterized

by the line position, intensity, half-width and contour. Moreover, Raman micro-mapping with

spatial resolution up to 1 µ allows one to get information about the material degree of

ordering, its homogeneity or heterogeneity on macro and micro-levels, and crystallite size.

In this report, the data on linear and spatial Raman micro-mapping would be

juxtaposed for graphites of various genesis (both natural and synthetic) and for other sp2-

carbons (glassy carbon, soot, nanotubes, fullerenes, shungite, carbine, graphene). Evaluation

of application of the widely used König correlation [1] would be also given.

[1] F. Tuinstra, J.L. Koenig. J. Chem. Phys. 53, 1126, 1970.

Acknowledgements -The authors acknowledge partial financial support of the Russian Foundation for Basic Research (project 10-03-01115)

e-mail: [email protected]


O4

KINETICS AND MECHANISM OF ALCOHOLS SUBSTITUTION IN THE CHROMIUM (III) COMPLEX of TETRAPHENYLPORPHIN

V.A.Burmistrov, I.P.Trifonova, A.V. Zaharov, O.I.Koifman

Ivanovo State University of Chemical Technology, Ivanovo, Russia

Metal complexes of porphyrins (MP) are the traditional synthetic objects modeling the

important biological macrocycles such as chlorophyll, haem and others. In solutions a metal ion as active center of MP is able to coordinate the molecules of the solvent. Thus the reaction of ligation in the 6-th coordination position of octahedral complex is the reaction of ligand exchange.

The study of solvent substitution in 6-th position of (acetate)tetraphenylporphyrinatochromium (III) complex ((AcO)CrTPP) by UV/Vis spectroscopy, 1H NMR and conductometry revealed that the axial coordination is the consecutive substitution of two alcohol molecules - at first from the outer coordination envelope and then – from the inner one. The high stability of alcohol dimer in axial position of octahedral complex is connected with strengthening of H-bond due to coordination of amphiprotic ligand by chromium (III). It provides the redistribution of electronic density from the second alcohol molecules to metal ion and the strengthening of the coordination bond.

The outer-sphere substitution of alcohol molecule on the stronger electronodonor – imidazole results in reinforcement of the Cr-ROH. The second lone pair of the last one is free and can participate in donor-acceptor interaction, particularly in H-bond formation with other alcohol monomer. On the base of inner-sphere substitution study the solvolytic associative-dissociative mechanism of axial exchange in 6-th coordination position of (acetate)tetraphenylporphirinatochromium (III) in amphiprotic environment was established. The main feature of the offered mechanism is the activation of an axial exchange by the interaction of a leaving ligand with a molecule of a solvent. The regression analysis of multifactor kinetic experiment was carried out, kinetic isotopic effects and activation parameters of process were studied. All regularities established for (AcO)CrTPP were found to be correct for (Cl)CrTPP as well.

The molecule of (chloro)chromium(III) porphyrin and its derivatives have been studied by density functional theory (DFT) computations utilizing the B3LYP hybrid method (Becke + Slater + HF exchange and LYP + VWN5 correlation). All calculations described above were performed using the PC GAMESS 7.1 version of the GAMESS software package. Major bond lengths (Cr-Cl, Cr-N in the pyrrole rings, and Cr-N or Cr-O in axial ligands) were obtained. Energies of Cr-O and Cr-N bonds were evaluated by the dividing the optimized structure of a complex with additional axial substituent into two across Cr-O or Cr-N bond and single-point energies of these parts ((chloro)chromium(III) porphyrin and the substituent) were calculated without reoptimizing the geometries. The sum of these energies was subtracted from the energy of the whole complex, thus giving the energy of homolytic bond breakage. According to our calculations the Cr-N bond in (chloro)chromium(III) porphyrin complex with imidazole is stronger than Cr-O bond in the ethanol complex both in systems with only one imidazole or ethanol ligand and in complexes with second imidazole or ethanol molecule attached to the first via hydrogen bonding. Therefore, the DFT computations unambiguously show that the substitution of ethanol with imidazole is energetically favorable that is in agreement with the experimental data. The intermediate complex with ethanol, imidazole, and a second ethanol molecule attached to both first ethanol and imidazole via two relatively weak hydrogen bonds, has significantly weaker Cr-O bond. e-mail: [email protected]


O5

SYNTHESIS OF NEW BENZOQUINONE-METHACRYLATES

S. Chesnokova, M.Shurygina a, M. Arsen’ev a, O. Markina a, N. Druzhkov a, V. Cherkasov a

aG. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA.

Metal-containing polymers are compounds with potentially wide area of application. Polymerization of monomers containing fragment which is able to bind metals can be the method of theirs synthesis. Quinoid structures are known to be used as ligands. The aim of this work is synthesis and investigation of properties of new methacrylate monomers containing sterically hindered benzoquinones; study of polymerization of benzoquinone-methacrylates and creating of metal-containing polymers on the basis of poly-o-quinones. Methacrylate monomers were synthesized by two ways. Exchange reaction of 3,6-di-tert-butyl-2-hydrogen-p-benzoquinone salts with chloride anhydride of methacrylate acid lead to formation p-benzoquinone-methacrylate (I) and o-benzoquinone-methacrylate (IIa) with total yield close to quantitative (Scheme 1). It was established that the ratio of products depends on reaction conditions.

solvent:THF, C6H6, CH3CN

O

OX

t-Bu

t-BuO H2C

H3C O

Cl

O

O

t-Bu

t-BuO

OCH3

CH2

I

Ot-Bu

t-BuO

OH3C

CH2O

IIa

solvent

X: Li, Na, K, Et3N, NBu4

-XCl

Scheme 1.

Alkoxylation of 3,6-di-tert-butyl-o-benzoquinone by hydroxymethacrylates was used for synthesis of four new o-benzoquinone-methacrylates with different hydrocarbon bridges (IIb-f, Scheme 2). All new p- and o-benzoquinone-methacrylate (I, IIa-f) were isolated and characterized.

t-Bu

t-Bu

O

OH2C

CH3O R

O

OH

H2C

CH3O R

O

O

t-Bu

t-Bu

O

O+

MnO2, KOH

DMFA, 500C

R= -(CH2)2- (b); -(CH2)4- (c); -(CH2)6- (d); CH2 CH2 (f).IIb-f

Scheme 2.

New poly-o-benzoquinones were obtained by thermal free-radical polymerization (AINA, 700С) of monomers IIb-f (in benzene and in bulk) and characterized. The polymers are well soluble in polar solvents and insoluble in hydrocarbons. The average number of links in polymer chain is 28-29 (polydispersity coefficient – 1.66). It was shown by EPR in solution that all poly-o-quinones are able to complexation. Poly-o-semiquinone complexes of manganese, copper, nickel and poly-catecholate of antimony were synthesis and characterized. Acknowledgements -This work was supported by the Russian Foundation for Basic Research (grant no 08-03-01045-a, 08-03-00668-a, 08-03-97055-r_povolzj’ye_a, 09-03-12268-ofi_m). e-mail: [email protected]


O6

THE MECHANISMS OF CATALYTIC REACTIONS WITH THE PARTICIPATION OF NORBORNADIENE

V. Flid, D. Dmitriev, E. Evstigneeva and R. Shamsiev

M. V. Lomonosov Moscow State Academy of Fine Chemical Technology, 119571, Vernadskogo pr., 86, Moscow, RUSSIA.

Different mechanisms of catalytic reactions with the participation of norbornadiene (NBD) are reported. They include allylation, dimerization, co-dimerization, etc. The catalysts of these reactions are the metals of 8B group of Periodic System mainly. The complex study with the use of different methods (NMR, IR, paramagnetic resonance spectroscopy, GC, GC-MS kinetics study), quantum-chemical calculation were performed for understanding of the mechanisms of the reactions with NBD participation. Nonconventional allylation of norbornenes and norbornadiene is the unique synthetic method allowing to introduce methylen-, vinyl- and methylenecyclobutane fragments in NBD structure. The reaction mechanism was offered for homogeneous and heterogeneous catalysts. β-Hydride transfer with participation both allylic and NBD fragments was confirmed by isotope methods. Ways of improving of the reaction parameters – usage of non-traditional reaction media (ionic liquids) and cluster-containing catalysts – had been studied [1,2]. Norbornadiene dimerization as well its co-dimerization with activated olefiens are very important and interesting reactions. Resulting dimers and co-dimers find a wide range of applications, including high-density high-energy jet fuel. The mechanism of the processes and factors affecting its stereo selectivity were thoroughly studied by kinetics, spectroscopic, and quantum chemical methods. The activation parameters found in quantum-chemical calculations are in the good agreement with the experimental ones. Key intermediates and possible equilibrium reactions were proposed; the specifics of regio- and stereo selectivity for different substrates were explained. The influence of the organophosphorous compounds as the additives to the catalytic systems allow increasing the selectivity of the reaction sharply. The role of phosphines in catalytic transformations, influence of electronic and steric factors of the ligand were established [3]. In the course of some reactions the paramagnetic Ni(I) intermediates were found. The theoretical and experimental study of its role in catalytic reactions was investigated. The time-concentration dependence of these intermediates was established. It was shown, that these complexes are very reactive. Their role in catalysis was proposed [4]. [1] E. Evstigneeva, V. Flid, Rus. Chem. Bul., 2008, 4, 823. [2] N. Tsukada, T. Sato, Y. Inoue, Tetrahedron Letters, 2000, 41, 4181. [3] I. Efros, D. Dmitriev, V. Flid, Kinetika i Kataliz, 2010, 3, 391 [4] Ya. Otman, O. Manulic, V.Flid. Kinetika i Kataliz, 2008, 49, 502. Acknowledgements – Russian Foundation for Basic Research Grant 08-03-00743 e-mail: [email protected]


O7

AB INITIO EVIDENCE FOR DITOPIC COORDINATION OF HETEROSILENES SI=E (E = C, N, O, SI, P, S) TO METHYLENE BRIDGED LIGAND CONTAINING

BOTH DONOR AND ACCEPTOR SITES

S.L. Guselnikova, V.G. Avakyana, V.F. Sidorkinb a Topchiev Institute of Petrochemical Synthesis, RAS, 119991 GSP-1, Moscow, RUSSIA

b Favorsky Irkutsk Institute of Chemistry, Siberian Branch of RAS, 664033, Irkutsk, RUSSIA Previously we reported a complexation of silene and dimethylsilene with ditopic ligands Me2N(CH2)nX (n = 0—2; X = BR2, SiR3, R = H, F, Cl) containing both donor and acceptor sites, studied at MP4/6-311G(d,p)//MP2/6-31G(d,p)+ZPE level of theory, to estimate their capability of simultaneously binding the silene moiety into the self-assembly complexes. Inasmuch as according to our predictions only silenes’ complexes with Me2NCH2SiF3 could have an interesting synthetical application, we extended our calculations to ditopic complexes of Me2NCH2SiF3 with heterosilenes Si=E (E = C, N, O, Si, P, S). The complexation energies were predicted as follows for E = C, N, O, Si, P, S, kcal/mol: –45.1, –53.6, –49.9, –23.3 (–21.3), –19.3, –21.6. The nature of bonding in the ditopic complexes of heterosilenes is the issue to discussion in terms of the structural and energetic parameters, supported by the data of the AIM and ELF topological analyses.

[1] Avakyan V.G. et al. Organometallics 2009, 28(4), 978-989. E-mail: [email protected]


O8

NEW TRANSFER HYDROGENATION CATALYSTS FOR CONVERSION OF ALCOHOLS INTO SECONDARY AMINES AND ESTERS.

D. Gusev and M. Bertoli

Department of Chemistry, Wilfrid Laurier University, 75 University Ave. W., ON N2L 3C5,

CANADA. This work deals with the synthesis, structure and reactivity studies of a series of outer-sphere transfer hydrogenation catalysts from our group, which are shown in the accompanying scheme:

The osmium complex 3 proved to be a particularly efficient transfer hydrogenation catalyst; it is also active for dehydrogenative coupling of primary alcohols. Without solvent, and using low catalyst loadings of 0.1 – 0.2 mol%, we observed high-yield formation of secondary amines from alcohols and primary amines or ammonia. A ring-closing reaction of 5-aminopentanol afforded piperidine:

Upon heating with 3, primary alcohols were converted into the corresponding esters, releasing two equivalents of hydrogen. This experimental research is supported by extensive NMR spectroscopic and DFT computational studies, and the mechanistic features of the catalytic reactions will be discussed. Acknowledgements - This work was made possible by the Natural Sciences and Engineering Research Council of Canada (NSERC), by the facilities of the Shared Hierarchical Academic Research Computing Network (SHARCNET: www.sharcnet.ca), and through the support by Wilfrid Laurier University e-mail: [email protected]


O9

Tb, Sm, and Eu COMPLEXES CONTAINING HETEROCYCLIC LIGANDS: PHOTO AND ELECTROLUMINESCENT PROPERTIES

Marina A. Katkova, Tatyana V. Balashova, Anatoly P. Pushkarev and Mikhail N. Bochkarev

G. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences,

603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA. Complexes of rare earth metals with organic ligands present an astounding class of emissive materials for OLEDs due to peculiarities of the luminescence properties. Their structure-property relationships can be used to recognize the fundamental characteristics of existing devices. The first step in this way is the understanding of the relation between their photoluminescent and electroluminescent properties. For this purpose lanthanide (Tb, Sm, and Eu) N,O-chelate complexes namely Ln(III)-tris-2-(2-benzoimidazol-2-yl)phenolate, Ln(III)-tris-2-(2-benzoxyazol-2-yl)phenolate, and Ln(III)-tris-2-(2-benzothiazol-2-yl)phenolate have been prepared and tested as photo- and electroluminescent compounds. PHOTO-

Ln = Tb3+ Sm3+ Eu3+

ELECTRO- Acknowledgements - This work was supported by the Russian Foundation of Basic Research (Grants, 10-03-00190, 09-03-97016) e-mail: [email protected]

450.0 480 500 520 540 560 580 600 620 650.00.0

100

200

300

400

500

600

700

800

860.0

nm

Tb

550.0 560 580 600 620 640 660 680 700.00.0

5

10

15

20

25

30

35

40

45

50

55.0

nm

Sm

570.0 580 590 600 610 620 630 640 650 660 670.00.0

2

4

6

8

10

12

14

16

18

20

22

24

26.0

nm

Eu

0

5 0

1 0 0

1 5 0

2 0 0

2 5 0

3 0 0

3 5 0

4 0 0

4 5 0 5 0 0 5 5 0 6 0 0 6 5 0

0

500

1000

1500

2000

2500

3000

3500

550 570 590 610 630 650 670 690

?

ITO 100 nmTPD 25 nm

Yb 150 nmLnR3 50 nm

N

O

O

NO

ON

O

OLn


O10

NEW APPROACH TO CONFORMATIONAL ANALYSIS OF SANDWICH COMPLEXES ON THE BASIS OF LASER THRESHOLD IONIZATION

SPECTROSCOPY COMBINED WITH DFT CALCULATIONS

S. Ketkova and H. Selzleb

aG. A. Razuvaev Institute of Organometallic Chemistry of Russian Academy of Sciences, 603950, Tropinina str, 49, Nizhny Novgorod, RUSSIA.

bTechnische Universität München, Lichtenbergerstr.4, Garching, GERMANY For over 50 years transition metal complexes with carbocyclic ligands ηn-CnHn (n = 4 - 8) and their substituted derivatives have been attracting chemists as one of the most interesting classes of organometallics. New possibilities appeared for studying sandwich electronic structures as modern variants of laser photoionization spectroscopy have been developed. The resonance enhanced multiphoton ionization (REMPI), zero kinetic energy (ZEKE) and mass-analyzed threshold ionization (MATI) techniques provide unprecedented resolution in measuring energies of electronic excited states and vibrational frequencies of polyatomic molecules. Interpretation of the results obtained with laser spectroscopy requires data on molecular parameters which can be obtained with high-level DFT calculations. This concerns especially the spectra of substituted sandwich systems revealing rotational isomers. Recently we reported the MATI spectrum of bis(η6-toluene)chromium in a supersonic jet1 assigned on the basis of BPW91/TZVP computations. The individual rotational isomers of the bisarene system in the gas phase have then been detected for the first time. In this presentation we summarize the new results of investigation of the (η6-Arene)2Cr (Arene = o,m,p-xylene, ethylbenzene, cumene, t-butylbenzene) systems by the laser threshold ionization spectroscopy combined with the DFT calculations. Supersonic cooling of organometallic molecules and employment of monochromatic laser radiation make it possible to achieve unique accuracy (± 5 cm-1) in determination of ionization energies (IEs) and vibrational frequencies. The data obtained correspond to free neutral molecules and cations so they can serve as a powerful experimental basis for verification of quantum chemical calculations. Our computations reveal different distributions of the rotational isomer relative energies for (η6-RPh)2Cr (R = Me, Et, i-Pr, t-Bu) and these differences agree very well with the experimental MATI peak separations and relative intensities. The spectra of the complexes with o- and m-xylene show three intense MATI bands in contrast to two strong peaks for the toluene derivative. The MATI spectrum of the EtPh complex shows two intense features like (η6-MePh)2Cr but their relative intensities are inverted. The spectra of the i-PrPh and t-BuPh complexes show only one MATI band. DFT explains these differences by the rotational isomer relative energies. The high-resolution ionization potentials of the sandwich compounds studied reveal a non-linear dependence of IEs on the number of methyl groups in the substituents. This effect arises from the changes in the zero point energies of the sandwich neutral molecules and cations. [1] S.Yu. Ketkov, H.L. Selzle, F.G.N. Cloke, Angew. Chem. Int. Ed. 2007, 46, 7072. Acknowledgements - This work was supported in part by RFBR (Projects 08-03-97054, 09-03-97045), Russian Ministry for Science and Education (Contract P-337), the Alexander von Humboldt Foundation and DFG. e-mail: [email protected]


O11

IRON PENTACARBONYL FOR ORGANIC SYNTHESIS – REAGENT, SOLVENT, CATALYST AND PROMOTER

K. A. Kochetkov, А. B. Тerent’ev, Т. Т. Vasil’eva, H. H. Hambardzumyan,

О. V. Chahovskaya, N. Е. Mysova, Н. Н. Tomashevskaya

A. N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991, Vavilova str, 28, Moscow, RUSSIA.

The use of transition metal assisted reactions is regarded as an area of current interest in organic chemistry. Most metal complexes widely used in the organic synthesis are either expensive or not easily available. On the other hand, iron oxides, salts and complexes are cheap and recently they have been proposed as catalysts and promoters for organic synthesis, at the same time the available metal carbonyls are used as reagents much more rarely. Really iron pentacarbonyl is a very cheap and widely spread compound.

Unfortunately during last years only several tens from more then 1600 reports using Fe(CO)5 have been dealing with synthetic organic chemistry, specifically isomerization, hydrogenation, carbonylation or transalkylation reactions. Most typically they have described Fe(CO)5 mediated isomerization of alkenes resulting in cyclo- or open structures via π-complexation of an iron carbonyl species to the double bond. The carbonylation, as well as hydrogenation, is also popular and can be achieved efficiently by coupling between RX and iron carbonyl

Documents

G.A. Razuvaev Institute of Organometallic Chemistry of RAS ... · International conference “Topical Problems of Organometallic and Coordination Chemistry” September 3-9, 2010,