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Chem 332 Organometallic Chemistry, Final Examination

Tuesday, May 24, 2005. Time allowed, 120 minutes. Total 100 points (plus 5 bonus points)
Section 1. Multiple Choices (22 points total). For each question, select the most appropriate answer by either writing it out or circling your choice.


1.1 Which of the following complexes is most reactive towards oxidative addition of CH3I?

a) CpCo(CO)2 b) CpRh(CO)2

c) CpIr(CO)2 d) [CpOs(CO)2]-


1.2 Which of the following oxidative addition reactions is/are least likely through a concerted mechanism?

a) IrI(CO)(PPh3)2 + ICH3 -----------> IrI2(CH3)(CO)(PPh3)2

b) IrI(CO)(PPh3)2 + HSiMe3 -----------> IrI(H)(SiMe3)(CO)(PPh3)2

c) IrI(CO)(PPh3)2 + H2-----------> IrI(H)2(CO)(PPh3)2

d) IrI(CO)(PPh3)2 + HCH3-----------> IrI(H)(CH3)(CO)(PPh3)2

e) more than one of them f) none of them


1.3 Which of the following oxidative addition reactions would you expect to occur at the highest reaction rate? Assuming non-concerted, SN2 pathway is involved in the reaction.

a) CpCo(CO)(PPh3) + CH3Br -----------> [CpCo(CH3)(CO)(PPh3)]Br

b) CpRh(CO)(PPh3) + CH3Br -----------> [CpRh(CH3)(CO)(PPh3)]Br

c) CpRh(CO)(PPh3) + t-BuBr -----------> [CpRh(t-Bu)(CO)(PPh3)]Br

d) CpCo(CO)(PPh3) + CH3CH2Br -----------> [CpCo(CH2CH3)(CO)2(PPh3)]Br


1.4 Which of the following oxidative addition reactions is least likely?



C)

1.5 Which of the following reactions would you expect to have the smallest equilibrium constant Keq?




a)
1.6 Which of the following ligands is/are chiral?


e) two of them f) three of them g) all of them h) none of them


1.7 Which of the following species could be used as the catalyst or catalytic precursor for the following reaction?




a) IrCl(PPh3)3 b) IrH3(PPh3)3 c) RuHCl(PPh3)3

d) NaH e) two of them f) three of them

g) all of them h) none of them 18e18e18e16e16e16e16e16e16e14e14e14e18e18e18e18e18e16e16e16e16e


1.8 Which of the following complexes could be used as the catalyst or catalytic precursor for the following reaction?




a) PdCl2 b) RhCl(PPh3)3

c) Cp2Ti=O d) CuCl2

e) two of them f) three of them

g) all of them h) none of them


1.9 Which of the following complexes could be used as the catalyst or catalytic precursor for the following reaction?




a) RhH(PPh3)3 b) (Ph3P)2Cl2Ru=CHPh

c) (RO)3WCCMe3 d) (PPh3)3RhCCCMe3

e) two of them f) three of them

g) all of them h) none of them


1.10 Which of the following complexes could be used as the catalyst or catalytic precursor for the following reaction?




a) Cp2ZrCl2/AlMe3 b) [RhCl(COD)]2/NEt3

c) Cp2(MeCN)Zr=CHCMe3 d) Rh(CCPh)(PPh3)3

e) two of them f) three of them

g) all of them h