Chem 1140; Introduction to Organometallic Chemistry

General Mechanistic Principles Reactions with Wilkinsons Catalyst

A. Organometallic Mechanisms

Oxidation State: The oxidation state of a metal is defined as the charge left on the metal after all ligands have been removed in their natural, closed-shell configuration. This is a formalism and not a physical property! d-Electron Configuration: position in the periodic table minus oxidation state.
18-Electron Rule: In mononuclear, diamagnetic complexes, the total number of electrons never exceeds 18 (noble gas configuration). The total number of electrons is equal to the sum of d-electrons plus those contributed by the ligands. 18 electrons = coordinatively saturated < 18 electrons = coordinatively unsaturated.

Cl Pd Cl bridging by lone pairs on Cl; each Cl acts as a 2-electron, mono negative ligands to one of the Pd's, and a 2-electron neutral donor ligand like PPh 3 to the other Pd

for each Pd: Ox. state

, Cl Pd(II)

d: 10 (4d10 5s 0) - 2 = 8 electron count: : 4e: 2e: 2e8e- + d 8 = 16eunsaturated

Cl Cl

H Zr Cl

Ox. State: 2 Cp -, 1 H-, 1 Cl Zr(IV) d: 4 (4d25s2) - 4 = 0 electron count: 2 Cp-: 12 H- : 2 Cl - : 2 Zr : 0 16 e-, unsaturated

Bonding considerations

donation: M vacant dsp hybrid or

backdonation: M

filled d orbital

for M-CO:

dsp n acceptor

donor

Structure

saturated (18 e-) complexes: - tetracoordinate: Ni(CO)4, Pd(PPh3)4 are tetrahedral - pentacoordinate: Fe(CO)5 is trigonal bipyramidal

- hexacoordinate: Cr(CO)6 is octahedral

z

unsaturated complexes have high dx2-y2; 16e- prefers square planar

Basic reaction mechanisms

- ligand substitution: M-L + L M-L + L can be associative, dissociative, or radical chain.

L + -

M + -

X + -

trans-effect: kinetic effect of a ligand on the role of substitution at the position trans to itself in a square or octahedral complex (ground-state weakening of bond). L M, repels negative charge to trans position.
Nu Lc Lt X Pt Lc + Nu Lc Lt X Pt Lc Lc Lt Lc Pt Nu X

Lc Lt

Pt X

Nu Lc

Lc Lt

Nu Pt Lc

+ X-

- oxidative addition:

-L [Ph3P]4Pd [Ph3P]3Pd 16 estrong -donor L2Pd H Br H Ph agostic (2e-/3-center bond) interactions 16 e-

-L [Ph3P]2Pd 14 e-

Ph

Br

(+II) Br L2Pd 16 ePh

- reductive elimination: the major way in which transition metals are used to make C,C- and C,H-bonds!

Me Ph3P

Pd

PPh3

Ph3P Ph3P

Pd

Me

-L

Ph3P

Pd

Me Ph3P-Pd 12ePh +L Ph

Ph

cis!

Ph

14e?

- migratory insertion:

Cp Zr Cp Cl 16e-

O CO R C

Cp Zr Cp Cl

R 16eO

Cp Zr Cp Cl

18e-

- -elimination/hydrometalation:

-elimination

H R

Cp Zr Cp Cl

H Cp Zr Cp Cl

Cp Cp H Zr Cl

hydrometalation

- olefin metathesis:

Fischer carbene complex OMe (OC) 5Cr 18ePh OEt , 80 C OMe + Ph (OC) 5Cr OEt

(OC) 5Cr EtO

OMe Ph

- transmetalation:

R-M + M-X

R-M + M-X

Summary of Mechanisms: - ligand substitution - oxidative addition/reductive elimination - migratory insertion/-elimination (carbo-, hydrometalation) - alkene metathesis - transmetalation

Reactions with Wilkinsons Catalyst

Alkene Hydrogenation
H2 cat. RhCl(PPh3)3 CO2Me CO2Me H2 cat. PtO2 96:4 49:26 CO2Me

Mechanism
PPh3 oxidative addition H Rh H Cl PPh3 coordination R PPh3 Cl Rh H PPh3

H H

[RhCl(PPh3)2]

-PPh3 +PPh3

RhCl(PPh3)3 R

reductive elimination R H R H H

PPh3 Cl Rh H PPh3

migratory insertion

Reductions

O i-PrOH, KOH cat. RhCl(PPh3)3

OH i-PrOH, KOH cat. RhCl(PPh3)3

OH

Where does the hydrogen come from????

Hydrosilylation

Et

or

Et

HSiMe2Ph cat. RhCl(PPh3)3

Et

SiMe2Ph

Hydrocarbonylation

THPO OTHP

0.4 equiv RhCl(PPh3)3 CHO CH2Cl2 40 oC, 20 h

H THPO H OTHP O

Decarbonylation

Et Ph O

1.0 equiv RhCl(PPh3)3

Et Ph H 93% retention

Hydroformylation

O N H

H2, CO cat. RhCl(PPh3)3 O N H other minor products CHO

Markownikow Hydroboration

1. catecholborane cat. RhCl(PPh3)3 Ph 2. H2O2, OHPh

OH

primary alcohol if the catalyst is partially oxidized

Cycloisomerization

H cat. RhCl(PPh3)3 TBDMSO TBDMSO H