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8/3/2019 Chem 373- Computational Chemistry As A Practical Tool in Molecular Science
1/63
Friday, March 31, 2000
Prof. Tom Ziegler - Department of Chemistry
University of Calgary-Calgary,Alberta,Canada T2N 1N4
Computational Chemistry As A Practical
Tool in Molecular Science"
Chemistry 373 University of Calgary
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EEEEaaaarrrrllllyyyy AAAAttttoooommmmiiiicccc tttthhhheeeeoooorrrryyyy
444400000000 bbbb....cccc....
JJJJoooohhhhnnnn DDDDaaaallllttttoooonnnn ((((1111777766666666---- 1111888844444444
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""""WWWWeeee aaaarrrreeee ppppeeeerrrrhhhhaaaappppssss nnnnoooottttffffaaaarrrrrrrreeeemmmmoooovvvveeeeddddffffrrrroooommmmtttthhhheeee
ttttiiiimmmmeeee wwwwhhhheeeennnn wwwweeee sssshhhhaaaallllllllbbbbeeee aaaabbbblllleeee ttttoooossssuuuubbbbmmmmiiiitttttttthhhheeee bbbbuuuullllkkkkooooffffcccchhhheeeemmmmiiiiccccaaaallllpppphhhheeeennnnoooommmmeeeennnnaaaa ttttooooccccaaaallllccccuuuullllaaaattttiiiioooonnnn....""""
----
JJJJoooosssseeeepppphhhh LLLLoooouuuuiiiissss GGGGaaaayyyy----LLLLuuuussssssssaaaacccc,,,,
MMMMeeeemmmmooooiiiirrrreeeessss ddddeeee llllaaaa SSSSoooocccciiiieeeetttteeeedddd''''AAAArrrrccccuuuueeeeiiiillll2222::::222200007777((((1111888800008888))))
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""""EEEEvvvveeeerrrryyyy aaaatttttttteeeemmmmppppttttttttoooo eeeemmmmppppllllooooyyyy mmmmaaaatttthhhheeeemmmmaaaattttiiiiccccaaaallll
mmmmeeeetttthhhhooooddddssss iiiinnnn tttthhhheeee ssssttttuuuuddddyyyy ooooffffcccchhhheeeemmmmiiiiccccaaaallllqqqquuuueeeessssttttiiiioooonnnnssss mmmmuuuussssttttbbbbeeee ccccoooonnnnssssiiiiddddeeeerrrreeeeddddpppprrrrooooffffoooouuuunnnnddddllllyyyyiiiirrrrrrrraaaattttiiiioooonnnnaaaallllaaaannnnddddccccoooonnnnttttrrrraaaarrrryyyy ttttoooo tttthhhheeee ssssppppiiiirrrriiiittttooooffffcccchhhheeeemmmmiiiissssttttrrrryyyy....
---- AAAA.... CCCCoooommmmtttteeee,,,, PPPPhhhhiiiilllloooossssoooopppphhhhiiiieeee
PPPPoooossssiiiittttiiiivvvveeee,,,, 1111888833330000....
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Quantum Wave-Mechanics
EEEErrrrwwwwiiiinnnn RRRRuuuuddddoooollllffffJJJJoooosssseeeeffff
AAAAlllleeeexxxxaaaannnnddddeeeerrrrSSSScccchhhhrrrrddddiiiinnnnggggeeeerrrr
1111888888887777----1111999966661111
WWWWeeeerrrrnnnneeeerrrrKKKKaaaarrrrllll
HHHHeeeeiiiisssseeeennnnbbbbeeeerrrrgggg1111999900001111----1111999977776666
H(ri)(ri)= E(ri)
i=1,3N
1926
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""""TTTThhhheeee uuuunnnnddddeeeerrrrllllyyyyiiiinnnnggggpppphhhhyyyyssssiiiiccccaaaallllllllaaaawwwwssss nnnneeeecccceeeessssssssaaaarrrryyyy ffffoooorrrrtttthhhheeee mmmmaaaatttthhhheeeemmmmaaaattttiiiiccccaaaalllltttthhhheeeeoooorrrryyyy ooooffff........tttthhhheeee wwwwhhhhoooolllleeee ooooffff
cccchhhheeeemmmmiiiissssttttrrrryyyy aaaarrrreeee tttthhhhuuuussss ccccoooommmmpppplllleeeetttteeeellllyyyy kkkknnnnoooowwwwnnnn,,,, aaaannnnddddtttthhhheeeeddddiiiiffffffffiiiiccccuuuullllttttyyyy iiiissss oooonnnnllllyyyy tttthhhhaaaatttttttthhhheeee eeeexxxxaaaaccccttttaaaapppppppplllliiiiccccaaaattttiiiioooonnnn oooofffftttthhhheeeesssseeee llllaaaawwwwssss lllleeeeaaaaddddssss ttttoooo eeeeqqqquuuuaaaattttiiiioooonnnnssss mmmmuuuucccchhhh ttttooooccccoooommmmpppplllliiiiccccaaaatttteeeeddddttttoooo ssssoooollllvvvveeee....""""
`P.A.M. Dirac(1929)
H(ri)(ri)= E(ri)
i=1,3N
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Exact Quantum Wave-Mechanics
H(ri)(ri)= E(ri)
i=1,3N
H (1926)H2+ (1929)
n!
He (1930)
H2 (1956)
Time requiredn! with number
of electrons n
C6H6 (2000)
Development
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Electron Correlation ?
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? ?
Exchange-correlation hole ?
8/3/2019 Chem 373- Computational Chemistry As A Practical Tool in Molecular Science
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Molecular Orbital Theory Diatomics Comparing MO and VBTheory
H H
A=1sA B=1sB
(1,2) =
1
2 [A(1) A(2)VBB B
( ) ( )]2 1+
H H
el. 1 el. 2
H H
el. 1el. 2
Both terms describe
a covalent Bond
(1,2) =1
2[(A(1) + A(2) +
= 12 A(1)B(2)+ 12 A(2)+ 12 A(1)A(2)+ 12B(1)B(2)
MO B B
B
( )( ( )]
( )
1 2
1
H H
el. 1 el. 2
H H
el. 1el. 2H H
el. 1
el. 2
ov. ov. Ionic
H H
el. 1
el. 2
Ionic
Equal
mixture ofionic andcovalent
bond
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Approximate Quantum Wave-Mechanics
HartreeAtomic Theory
R.K.MullikanMolecular Orbital theory
Some too good
to be true
Some theories are tootrue to be good
L.Pauling J. PopleSystematic ImprovementsValence Bond theory
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AAAApppppppprrrrooooxxxxiiiimmmmaaaatttteeee WWWWaaaavvvveeee mmmmeeeecccchhhhaaaannnniiiiccccssss
Hartree Fock (2000 atoms)
log(t)
2
Mller-Plesset (100 atoms)4
Quadratic CI ( 10 atoms)
DDDDeeeeaaaaddddEEEEnnnndd
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DDDDeeeennnnssssiiiittttyyyy FFFFuuuunnnnccccttttiiiioooonnnnaaaalllltttthhhheeeeoooorrrryyyy
TTTThhhhoooommmmaaaassss----FFFFeeeerrrrmmmmiiii----DDDDiiiirrrraaaacccc ((((1111999922229999))))
Model expression of total energy in
terms of electron density
E()
Fermi
W. Kohn
KKKKoooohhhhnnnn----HHHHoooohhhheeeennnnbbbbeeeerrrrgggg----SSSShhhhaaaammmm ((((1111999966664444))))Exact relationship between electrondensity and molecular energy ..
..but, form of relationship not known
E()
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? ?
Exchange-correlation hole ?
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Approximate density
functional theoriesfor exchange and correlation
HFSLocal exchange
LSDLocal exchange +Local correlation
LSD/NLLocal exchange +
Local correlation
+ Nonlocal corrections
Exchange energy
from electron gas
Exchange+correlationfrom electron gas
Nonlocal Exchange:Becke,A.D. Phys.Rev. 1988,A38
Nonlocal CorrelaionPerdew,J. Phys.Rev. 1986,B33
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Approximate density
functional theoriesfor exchange and correlation
HFSLocal exchange
LSD
Local exchange +Local correlation
LSD/NLLocal exchange +
Local correlation
+ Nonlocal corrections
Exchange energy
from electron gas
Exchange+correlationfrom electron gas
Nonlocal Exchange:Becke,A.D. Phys.Rev. 1988,A38
Nonlocal CorrelaionPerdew,J. Phys.Rev. 1986,B33
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NNNNoooobbbbeeeellllPPPPrrrriiiizzzzeeeessss iiiinnnn CCCChhhheeeemmmmiiiissssttttrrrryyyy
1998
Walter Kohn
E() E =
E()
John Pople
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ACCURATE STRUCTURESFOR ACCURATE EXPECTATION
VALUES
Reactant(s)
Product(s)
TransitionState
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Metal-ligand bond distancesfrom HF and Xa calculations
Mol Bond HF Xa EXP
Fe(Cp)2 Fe-Cp 1.88 1.60 1.65
Fe(CO)5 Fe-COax 2.04 1.774 1.80
Fe-COeq 1.874 1.798 1.827
Ni(CO)4 Ni-CO 1.921 1.794 1.838
Cr(CO)6 Cr-C 2.00 1.868 1.914
Fan and Ziegler ,J.Chem.Phys. 1991,95,7401
Fe Cr
CO
OC CO
OC
CO
CO
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Metal-ligand bond distances
from LDA and LDA/NL calculations
Mol Bond LDA(HFS) LDA/NL EXP
Fe(Cp)2 Fe-Cp 1.59 1.65 1.66
Fe(CO)5 Fe-COax 1.768 1.817 1.807
Fe-COeq 1.769 1.814 1.827
Ni(CO)4 Ni-CO 1.795 1.841 1.838
Cr(CO)6 Cr-C 1.872 1.909 1.914
Fan and Ziegler ,J.Chem.Phys. , 1991,95,7401
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O
O
O O
C
C C
O O
C C
FeFe
C
C
C C
O
O O
252.3252.3
182.5183.6
114.8115.6
201.1201.6
116.8117.6
77.7
77.6
96.096.1
NL - SCF
Experiment
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C
C
C
C
C
AlO
AlO
C
C
C
C
Zr
Al
O
C
C
C
O
C
Al
C
C
C
O
C
Al
C
C
O
Al
C
C
C
AAAAccccttttiiiivvvvaaaattttiiiioooonnnn ooooffffccccaaaattttaaaallllyyyysssstttt
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BBBBiiiioooollllooooggggiiiiccccaaaallllmmmmoooolllleeeeccccuuuulllleeeessss
MMMMeeeettttaaaallllSSSSuuuurrrrffffaaaacccceeeessssSSSSoooolllliiiiddddssss
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ACCURATEENERGETICS
Reactant(s)
Product(s)
TransitionState
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Molecule HFS LDA LDA/NL Exp
Cr(CO)6 278 276 193 192/155
Mo(CO)6
226 226 166 170
W(CO)6 247 249 183 192
Fe(CO)5 267 263 192 176
Ni(CO)4 194 192 121 104
First metal-Carbon Dissociation Energy
Li+Schreckenbach+ZieglerJ.Am.Chem.Soc,Sunmitted
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10
20
30
40
a
OO
E
(kcal/mol)
10
20
30
40
Ni Pd Pt
Ni Pd Pt
c
E
(kcal/mol)
10
20
30
40
Ni Pd Pt
Fe Ru Os
d
10
20
30
40
b
Relativistic influence
: non-relativistic : relativisticLi+Ziegler, Inorg.Chem, submitted
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Energetics ???
Vibrations
BondBreaking
Conformations
ExcitationsIonizations
andAffinities
Spin-flip
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BBBBiiiioooollllooooggggiiiiccccaaaallllmmmmoooolllleeeeccccuuuulllleeeessss((((HHHHuuuuddddrrrrooooggggeeeennnn BBBBoooonnnnddddSSSSttttrrrreeeennnnggggtttthhhh))))
MMMMeeeettttaaaallllSSSSuuuurrrrffffaaaacccceeeessss((((AAAAddddssssoooorrrrppppttttiiiioooonnnn EEEEnnnneeeerrrrggggiiiieeeessss))))
SSSSoooolllliiiiddddssss((((CCCCoooohhhheeeessssiiiivvvveeee EEEEnnnneeeerrrrggggyyyy))))
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H
E
hv
Cl
C
C
C
C
C
Si Zr
C
C
C
C
Cl
C
Inorganic Spectroscopy
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EXCITED STATES
Photo Chemistry
hv
Electron Transfer
Ziegler,Rauk,BaerendsTheor.Chim.Acta
1977,43,261
Excitations
V Ch T f
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cm-1
}Oxygent1
4t2a1
Metal-d5t2e
Orbital Diagram
0
1
2
3
4
5
6
a1-5t2
3t2-e
4t2-5t2
t1-5t2
4t2-e
t1-e
AOC
Determinants
only
1T2
1T2
1T2
1T2
1T2
1T21T1
1T1
1T1
1T1
1T1
50 000
40 000
30 000
20 000
10 000
eV
0
sharp
broad
sharp
broad
broad
weak
Experime
nt
Determinants
andintegrals
Ground state
3T13T2
cm -1
Charge TransferSpectrumof Permanganate
R.Dickson + T.Ziegler, Int. J. Quantum Chem., 1995
Mn
O O
O O
ACCURATE
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ACCURATEFORCE FIELDS
Entropy of activation
Spectroscopic finger printing
Molecular Mechanics Force Fields
A.Berces and T.ZieglerTopics in Current Chemistry
Springer 1996
Vibrations
no LDA Exp no LDA Exp
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Calculated and
observedvibrational
frequ nciesof ferrocene
no. LDA Exp. no. LDA Exp.
A 1'
1 3161 3110 E1' 17 3155 30773 1086 1102 18 1371 1410
2 791 814 20 978 10054 305 309 19 808 855
21 489 492A1" 5 1209 1255 22 163 179
6 44 44E2' 23 3138 3100
A2' 7 1210 1250 26 1318 135624 1014 1058
A2" 8 3162 3103 25 838 897d10
1088 111027
790 d9 777 820 28 562 59711 458 478
E2" 29 3139 3085E1" 12 3153 3086 32 1337 1351
13 1370 1410 30 1025 105515 966 998 31 845 885d14 770 844 33 814 d16 362 389 34 560 569
A.Berces+T.Ziegler J.Phys.Chem 1994
Fe
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NMR-SPECTROSCOPY
SpectroscopicFinger printing
SHIFTS:Schreckenbach+Ziegler
Phys.Chem. 1995
Spin-Spin CouplingDickson+ZieglerPhys.Chem. 1996
Spin-flipNMR/ESR
NMR/ESR
Spin-spin coupling
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-1000
-800
-600
-400
-200
0
17Oa
bsoluteshielding(pp
m)
[CrO4]2- [MoO
4]2- [WO
4]2-
Experiment
non-rel
rel
[MnO4]- [TcO
4]- [ReO
4]-
Experiment
non-rel
rel
RuO4
OsO4
non-rel
rel
Experiment
17O shieldings in transition metal oxides [MO4]n-
Inorganic Tellurium shifts
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-1000
-500
0
500
1000
1500
2000
2500
3000
-1000-500 0 500 1000 1500 2000 2500 3000
Calculated
(ppm
)
Experiment (ppm)
[Te 4]2+(cyclic)
TeSe 32-
[TeCl 6]2-
[TeBr 6]2-
Te=P(i
Pr)3
Te=P(CH 3)3
[Te 6]4+(cyclic)
Te(OH) 6
TeF6
CH3OTeF6-
Inorganic Tellurium shifts
O t lli T ll i hift
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Organometallic Tellurium shifts
-1000
-500
0
500
1000
1500
2000
2500
3000
-1000-500 0 500 1000 1500 2000 2500 3000
C
alculated(p
pm)
Experiment (ppm)
M
Te
Te
PMe3
PMe3
Me3P
Me3P
M=W
M=Mo
Cl Pd Cl
Te
Te
trans-[Pd{Te(CH2)4}2Cl2]
Te
Fe Fe
Te
CO
CO
CO
OC
OC
OC
CH3
CH3Fe2(CO)6(-TeMe)2 CH3
CH3
CH3H3C
H3C
Re
TeHOCCOH
[Cp*Re(CO)2H(TeH)]
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METAL-NMR SHIFTS
Compound NMR Chemical Shifts
Calculated
Non- RelRel
Exp
Cr(CO)6 -1.824 -1.810 -1.795
Mo(CO)6
-1.807 -1.965 -1.857
W(CO)6 -4.030 -3.619 -3.505
Schreckenbach+Ziegler Int.J.Quant.Chem. , 1997,61,899
Reduced K(M C) Coupling Constants
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Molecule K(M-C)
Cal. Exp.
V(CO) 6 - 1 2 9 1 4 6Fe(CO) 6 2 2 0 2 3 9
Co(CO)4- 3 4 8 3 8 0
Mo(CO) 6 2 9 3 3 4 4Nb(CO)6
- 2 6 2 3 1 9
Rh(CO)4- 7 1 3 7 7 8
W(CO) 6 8 1 6 9 9 7
Reduced K(M-C) Coupling Constants
1019 Kg m-2 s-2 A-2 Khandogin+Ziegler
Spectrochim. Acta1999,55,607
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EPR g tensors in d1 porphyrine complexes of
3d transition metals
g||
g
g
E: O, N, S, Se
L: Cl, H2O, none
M: V, Cr
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M E
Isotropic g values
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BBBBiiiioooollllooooggggiiiiccccaaaallllmmmmoooolllleeeeccccuuuulllleeeessss((((EEEESSSSRRRRooooffffmmmmeeeettttaaaalllllllloooo----pppprrrrooootttteeeeiiiinnnnssss))))
MMMMeeeettttaaaallllSSSSuuuurrrrffffaaaacccceeeessss((((IIIIrrrrooooffffaaaabbbbssssoooorrrrbbbbeeeeddddmmmmoooolllleeeeccccuuuulllleeeessss))))
SSSSoooolllliiiiddddssss((((NNNNMMMMRRRRooooffffSSSSoooolllliiiiddddssss))))
AAAAssssttttrrrroooonnnnoooommmmyyyy ((((MMMMoooolllleeeeccccuuuulllleeeessss iiiinnnn oooouuuutttt----ssssppppaaaacccceeee))))
Static DFT Calculations
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Static DFT Calculations
Localizing Stationary Points
Tracing Reaction Path
Reactant(s)
Transition State
Product(s)
ADF-Program by Baerends et al.
Local Spin Density Approximation +BP86
Calgary extensions
Alcohol Oxidation
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CrCl2O2 + CH3OH CrCl2(OH)2+ CH2O
+
Ha
a
b
cd
e
f
g
h
i
TS1
co o O da oO-H Addition
#
Reactants
Addition Product
IRC for O-H
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IRC for O-HBond Addition
Deng+Ziegler, Jacs 1996
1.0
2.0
3.0
-20
40
140
Distances(ng
stroms)
Ang
les(Degree
s)
0.0-10.0 10.0
Ha
a
bcd
e
fg
h
i
f g
b
ihca
c
fcb
IRC for O-H
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IRC for O HBond Addition
Deng+Ziegler, Jacs 1996
1.0
2.0
3.0
-20
40
140
Distances(ng
stroms)
Ang
les(Degree
s)
0.0-10.0 10.0
Ha
a
bcd
e
fg
h
i
f g
b
ihca
c
fcb
Dynamic DFT Calculations
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y
Slow-growths Dynamics:
First principle dynamics byCar-Parrinello procedure
Reactant(s)
Transition State
Product(s)
Projector Augmented wave method
Local Spin Density Approximation +BP86
Draging system along reactioncoordinate. Full dynamicsperpendicular to reaction coordinate
P.Blchl Phys.Rev B 1994,B 50, 17953
Alkane Carbonylation
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ClRh
PH 3
H3PH
CH3
5
ClRh
PH 3
H3P
H
CH3
OC
10
#
H CH3
OCl Rh
PH3
H3P 2
14-e-
ClRh
PH 3
H3P HCH3
#
4
ClRh
PH3
H3P
H
HC
H
H
3
+ CH4
ClRh
PH3
H3P
H
CH3
CO
6 + CO
ClRh
PH3
H3PH
CH3O
ClRh
PH 3
H3PH
CH3O
CO
ClRh
PH3
H3P H
CH3
O
CO
11
12
13
#
+ CO
Cl Rh
PH3
H3P
1
14-e-
-CO
h
-CO
CO+CH4
H CH3
O
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Alkane Carbonylation
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ClRh
PH 3
H3PH
CH3
5
ClRh
PH 3
H3P
H
CH3
OC
10
#
H CH3
OCl Rh
PH3
H3P 2
14-e-
ClRh
PH 3
H3P HCH3
#
4
ClRh
PH3
H3P
H
HC
H
H
3
+ CH4
ClRh
PH3
H3P
H
CH3
CO
6 + CO
ClRh
PH3
H3PH
CH3O
ClRh
PH 3
H3PH
CH3O
CO
ClRh
PH3
H3P H
CH3
O
CO
11
12
13
#
+ CO
Cl Rh
PH3
H3P
1
14-e-
-CO
h
-CO
CO+CH4
H CH3
O
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Alkane Carbonylation
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ClRh
PH 3
H3PH
CH3
5
ClRh
PH 3
H3P
H
CH3
OC
10
#
H CH3
O Cl RhPH
3
H3P 2
14-e-
ClRh
PH 3
H3P HCH3
#
4
ClRh
PH3
H3P
H
HC
H
H
3
+ CH4
ClRh
PH3
H3P
H
CH3
CO
6 + CO
ClRh
PH3
H3PH
CH3O
ClRh
PH 3
H3PH
CH3O
CO
ClRh
PH3
H3P H
CH3
O
CO
11
12
13
#
+ CO
Cl Rh
PH3
H3P
1
14-e-
-CO
h
-CO
CO+CH4
H CH3
O
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Alkane Carbonylation
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ClRh
PH 3
H3PH
CH3
5
ClRh
PH 3
H3P
H
CH3
OC
10
#
H CH3
O Cl Rh
PH3
H3P 2
14-e-
ClRh
PH 3
H3P HCH3
#
4
ClRh
PH3
H3P
H
HC
H
H
3
+ CH4
ClRh
PH3
H3P
H
CH3
CO
6 + CO
ClRh
PH3
H3PH
CH3O
ClRh
PH 3
H3PH
CH3O
CO
ClRh
PH3
H3P H
CH3
O
CO
11
12
13
#
+ CO
Cl Rh
PH3
H3P
1
14-e-
-CO
h
-CO
CO+CH4
H CH3
O
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Alkane Carbonylation
Alkane Carbonylation
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ClRh
PH 3
H3PH
CH3
5
ClRh
PH 3
H3P
H
CH3
OC
10
#
H CH3
O Cl Rh
PH3
H3P 2
14-e-
ClRh
PH 3
H3P HCH3
#
4
ClRh
PH3
H3P
H
HC
H
H
3
+ CH4
ClRh
PH3
H3P
H
CH3
CO
6 + CO
ClRh
PH3
H3PH
CH3O
ClRh
PH 3
H3PH
CH3O
CO
ClRh
PH3
H3P H
CH3
O
CO
11
12
13
#
+ CO
Cl Rh
PH3
H3P
1
14-e-
-CO
h
-CO
CO+CH4
H CH3
O
Cl
Rh
PH3
H3
P
H
CH3
5
Cl
Rh
PH3
H3P
H
CH3
O
C
#
H CH3
O
ClRh
PH3
H3
P2
14-e -
Cl
Rh
PH3
H3P
H
CH3
#
4
Cl
Rh
PH 3
H3P
H
HC
H
H
3
+ CH4
Cl
Rh
PH3
H3
P
H
CH3
CO
+ CO
Cl
Rh
PH3
H3
P H
CH3O
Cl
Rh
PH3
H3P
H
CH 3O
CO
Cl
Rh
PH3
H3
PH
CH3
O
CO
11
12
13
#
+ CO
ClRh
PH3
H3
P
1
14-e -
-CO
h
-CO
RRRReeeellllaaaattttiiiivvvveeee eeeennnneeeerrrrggggiiiieeeessss aaaannnnddddssssttttrrrruuuuccccttttuuuurrrreeeessssooooffffaaaallllllllssssppppeeeecccciiiieeeessss iiiinnnnvvvvoooollllvvvveeeedddd
RRRRaaaatttteeee ddddeeeetttteeeerrrrmmmmiiiinnnniiiinnnnggggsssstttteeeepppp
IIIInnnnssssiiiigggghhhhttttffffoooorrrrmmmmooooddddiiiiffffiiiiccccaaaattttiiiioooonnnnssss aaaannnnddddiiiimmmmpppprrrroooovvvveeeemmmmeeeennnnttttssss
Scope of Catalytic Investigation
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1. CO + C2H4 + H2Rh,Co
C OH3C
H
2.
Hydroformylation
CO + C2H4Pd,Ni
O
O
O
O
3. MeOH + CORh,Ir
C OH3C
OH
Acetic Acid
4. CH4 + CORh
C OH3C
H
5. C2H4 + HX
p y g
X
H H H
HH
Olefin addition X=H,B(OR)2:TeR
6.
R
'R
Rh
Cr,MoR
+
'R
Metathesis
Olefin Polymerization Catalysis
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Cp2M-RCH2=CHCH3
Cp2M-CH
2CH(CH
3)R
Propagation
Cp2M-RH2
Cp2M-H + RH
Termination and Chain Transfer
Termination and Chain Transfer
Cp2M-CH2CH(CH3)R H
Cp2M-H + CH2=C(CH3)R
Termination by CH activation
Cp2M-R
Cp2M-CH=C(CH3)R + RH
CH2=CHCH3
T.K.Woo,L.Fan,T.Ziegler:Organometallics 1994,13,432; 13,2253
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Cobalt
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Computerson benches
all linkedtogether