INORGANIC TUTORIAL 4

1. Classify the following reactions as oxidative addition, reductive elimination, migratory

insertion, -elimination, ligand coordination change, or simple addition.
(a) [RhI3(CO)2CH3]- → {RhI3(CO)(solvent)[C(O)CH3]}-
(b) Mn2(CO)10 + Br2 → 2 MnBr(CO)5
(c) Ir(PPh2Me)2(CO)Cl + CF3I → Ir(CF3)(I)(PPh2Me)2(CO)Cl
(d) TiCl4 + 2 Et3N → TiCl4(NEt3)2

2. Which among the following compounds will not undergo oxidative addition of methyl
iodide? Give reasons.
(a) Ir(PPh3)2(CO)Cl
(b) [RhI2(CO)2]−
(c) 5-Cp2Ti(Me)Cl

3. Mark against each statement the appropriate type of reaction or reactions from the list
(oxidative addition, reductive elimination, migratory insertion, and -H transfer)
(a) cis-Orientation of the participating ligands is a must
(b) This reaction does not occur for d0 metal complexes
(c) This reaction is enthalpy favored and entropy prohibited
(d) Vacant coordination site(s) in the metal center is a prerequisite
(e) The more electron-rich the metal center, the more facile the reaction
(f) There is an increase in metal electron count by two units during this reaction

4. Consider the following reaction.

+ ex. CO + (H3 C)2CO

Co Co
Ph3 P
Me OC CO
Me

The most plausible sequence of mechanistic steps for the reaction is:
(I) (a) Loss of phosphine (b) addition of CO (c) insertion of CO (d) addition of excess CO
with reductive elimination of acetone
(II) (a) Addition of CO (b) loss of phosphine (c) insertion of CO (d) addition of excess CO
 with reductive elimination of acetone
(III) (a) addition of CO (b) insertion of CO (c) reductive elimination of acetone (d)
addition of CO (e) loss of phosphine
(IV) (a) Loss of phosphine (b) addition of CO (c) addition of CO (d) reductive elimination
of acetone (e) addition of CO

5. Which one among the following compounds is least likely to undergo reductive
elimination?
(a) 5-Cp2Ti(n-Bu)H
(b) [(CO)2I3Rh(CO)Me]−
(c) (PPh3)2Pt(Me)H
(d) 5-Cp2Nb(H)(2-C2H4)

6. The given metal-alkane intermediate is unstable and undergoes a rearrangement

resulting in the formation of two different aryl-alkene complexes of the general formula
Pd(PPh3)2(Br)(H)(2-aryl-alkene). Predict the structures of the two aryl-alkene palladium
complexes.

Br PPh3

Pd
Ph
Ph3 P

7. HCo(CO)3 (formed from HCo(CO)4 by the loss of CO) catalyzes the reaction of propylene
(CH3CH=CH2) with CO and H2. The product of this reaction is butyraldehyde
(CH3CH2CH2CHO). Draw a suitable catalytic cycle by considering that in the conversion,
the following reactions [(a) to (f)] occur in the given sequential order.
(a) ligand addition/coordination, (b) 1,2-migratory insertion, (c) ligand
addition/coordination, (d) 1,1-migratory insertion, (e) oxidative addition, and (f)
reductive elimination.
8. The reaction of compound A (R = Ph) with an excess of CO in benzene afforded
compound B. Write a suitable mechanism for this conversion.

9. The reaction of Schwartz’s reagent, Cp2Zr(Cl)(H) (A), with trans-but-2-ene affords

terminal alkyl group containing compound, Cp2Zr(Cl)(CH2CH2CH2CH3) (B), out of
hydrozirconation (defined as the insertion of terminal or internal alkene into Zr-H bond).
Sketch the reaction sequence that converts compound A to B.

10. Compound A, called “Crabtree Catalyst,” catalyzes the hydrogenation of alkenes. Here,
the COD gets hydrogenated to cyclooctene (as in compound B) and then to cyclooctane,
which leaves the metal to generate the active form of the catalyst C. Species B and C
have one and two weakly coordinating solvent molecules, respectively. Write clearly the
steps involved in the formation of compound B from A.

11. Thermal degradation of compound A gives C2H6 as the major product. However, it’s
doubly oxidized species, compound B, under the same thermal degradation condition,
affords C4H10 as the major product. Offer a suitable explanation for these observations.