chem 373- computational chemistry as a practical tool in molecular science

8/3/2019 Chem 373- Computational Chemistry As A Practical Tool in Molecular Science

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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


2/63

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444400000000 bbbb....cccc....

JJJJoooohhhhnnnn DDDDaaaallllttttoooonnnn ((((1111777766666666---- 1111888844444444


3/63

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----

JJJJoooosssseeeepppphhhh LLLLoooouuuuiiiissss GGGGaaaayyyy----LLLLuuuussssssssaaaacccc,,,,

MMMMeeeemmmmooooiiiirrrreeeessss ddddeeee llllaaaa SSSSoooocccciiiieeeetttteeeedddd''''AAAArrrrccccuuuueeeeiiiillll2222::::222200007777((((1111888800008888))))


4/63

""""EEEEvvvveeeerrrryyyy aaaatttttttteeeemmmmppppttttttttoooo eeeemmmmppppllllooooyyyy mmmmaaaatttthhhheeeemmmmaaaattttiiiiccccaaaallll

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---- AAAA.... CCCCoooommmmtttteeee,,,, PPPPhhhhiiiilllloooossssoooopppphhhhiiiieeee

PPPPoooossssiiiittttiiiivvvveeee,,,, 1111888833330000....


5/63

Quantum Wave-Mechanics

EEEErrrrwwwwiiiinnnn RRRRuuuuddddoooollllffffJJJJoooosssseeeeffff

AAAAlllleeeexxxxaaaannnnddddeeeerrrrSSSScccchhhhrrrrddddiiiinnnnggggeeeerrrr

1111888888887777----1111999966661111

WWWWeeeerrrrnnnneeeerrrrKKKKaaaarrrrllll

HHHHeeeeiiiisssseeeennnnbbbbeeeerrrrgggg1111999900001111----1111999977776666

H(ri)(ri)= E(ri)

i=1,3N

1926


6/63

""""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


7/63

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


8/63

Electron Correlation ?


9/63

? ?

Exchange-correlation hole ?


10/63

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


11/63

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


12/63

AAAApppppppprrrrooooxxxxiiiimmmmaaaatttteeee WWWWaaaavvvveeee mmmmeeeecccchhhhaaaannnniiiiccccssss

Hartree Fock (2000 atoms)

log(t)

2

Mller-Plesset (100 atoms)4

Quadratic CI ( 10 atoms)

DDDDeeeeaaaaddddEEEEnnnndd


13/63

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()


14/63

? ?

Exchange-correlation hole ?


15/63

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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17/63

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


19/63

ACCURATE STRUCTURESFOR ACCURATE EXPECTATION

VALUES

Reactant(s)

Product(s)

TransitionState


20/63

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


21/63

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


22/63

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


24/63

BBBBiiiioooollllooooggggiiiiccccaaaallllmmmmoooolllleeeeccccuuuulllleeeessss

MMMMeeeettttaaaallllSSSSuuuurrrrffffaaaacccceeeessssSSSSoooolllliiiiddddssss


25/63

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


28/63

Energetics ???

Vibrations

BondBreaking

Conformations

ExcitationsIonizations

andAffinities

Spin-flip


29/63

BBBBiiiioooollllooooggggiiiiccccaaaallllmmmmoooolllleeeeccccuuuulllleeeessss((((HHHHuuuuddddrrrrooooggggeeeennnn BBBBoooonnnnddddSSSSttttrrrreeeennnnggggtttthhhh))))

MMMMeeeettttaaaallllSSSSuuuurrrrffffaaaacccceeeessss((((AAAAddddssssoooorrrrppppttttiiiioooonnnn EEEEnnnneeeerrrrggggiiiieeeessss))))

SSSSoooolllliiiiddddssss((((CCCCoooohhhheeeessssiiiivvvveeee EEEEnnnneeeerrrrggggyyyy))))


30/63

H

E

hv

Cl

C

C

C

C

C

Si Zr

C

C

C

C

Cl

C

Inorganic Spectroscopy


31/63

EXCITED STATES

Photo Chemistry

hv

Electron Transfer

Ziegler,Rauk,BaerendsTheor.Chim.Acta

1977,43,261

Excitations

V Ch T f


32/63

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


33/63

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


34/63

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


35/63

NMR-SPECTROSCOPY

SpectroscopicFinger printing

SHIFTS:Schreckenbach+Ziegler

Phys.Chem. 1995

Spin-Spin CouplingDickson+ZieglerPhys.Chem. 1996

Spin-flipNMR/ESR

NMR/ESR

Spin-spin coupling


36/63

-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


37/63

-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


38/63

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)]


39/63

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


40/63

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


41/63

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


42/63

M E

Isotropic g values


43/63

BBBBiiiioooollllooooggggiiiiccccaaaallllmmmmoooolllleeeeccccuuuulllleeeessss((((EEEESSSSRRRRooooffffmmmmeeeettttaaaalllllllloooo----pppprrrrooootttteeeeiiiinnnnssss))))

MMMMeeeettttaaaallllSSSSuuuurrrrffffaaaacccceeeessss((((IIIIrrrrooooffffaaaabbbbssssoooorrrrbbbbeeeeddddmmmmoooolllleeeeccccuuuulllleeeessss))))

SSSSoooolllliiiiddddssss((((NNNNMMMMRRRRooooffffSSSSoooolllliiiiddddssss))))

AAAAssssttttrrrroooonnnnoooommmmyyyy ((((MMMMoooolllleeeeccccuuuulllleeeessss iiiinnnn oooouuuutttt----ssssppppaaaacccceeee))))

Static DFT Calculations


44/63

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


45/63

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


46/63

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


47/63

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


48/63

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


49/63

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


50/63



51/63

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


52/63



53/63

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


54/63



55/63

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


56/63




57/63

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

chem 373- computational chemistry as a practical tool in molecular science

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