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Wilkinson Final
Wilkinson Final
O O
CH3 C C
R2 R2 Ph3P PPh3
R3P CO P Cl P
Rh
Re Mo Mo
PR3 P Cl P Ph3P Cl
R2 C C R2
CO
O O
1
Organometallic Compound: Looking closer
Molecular Hydrogen: H2 H
M
H
Hydride H- M-H
Carbonyl: C≡O M C O
Alkene M
H2C CH2
2
3
Catalysis : Basics
Heterogeneous Ea
Ea
Homogeneous catalyzed
∆G
4
Catalysis : Why
5
How to select a good catalyst?
6
7
Good Catalysts
9
10
11
Hydrogenation of Unsaturated Hydrocarbons
H H
-CH=CH- + H2 → -CH-CH-
NOBEL : 2001
12
Wilkinson’s Catalyst (WC)
Ph3P PPh3
Rh
Cl PPh3
Chlorotris(triphenylphosphine)rhodium(I)
square planar d8 configuration
13
Geoffrey Wilkinson
• Born July 14, 1921, Yorkshire, England
• Ph.D from Cal Berkeley studying with Glenn Seaborg
• First published compound in 1965 in Journal of the
Chemical Society - Chemical Communications
•Nobel Prize in Chemistry 1973 (shared with Ernst
Otto Fischer) for their pioneering work, performed
independently, on the chemistry of the organometallic,
so called sandwich compounds.
14
Synthesis of WC
Ph3P PPh3
EtOH
RhCl3 + 3 H2O + >4 PPh3 Rh + Ph3PO
78 oC
Cl PPh3
Commercially available
15
WC in alkene Hydrogenation: Catalytic Steps
(1) Oxidative addition
H
Ph3P PPh3 Ph3P PPh3
Rh + H2 Rh
Ph3P Cl Ph3P H
Rh+1 Cl
Rh3+
(2) Ligand Dissociation
H
H
Ph3P PPh3 Ph3P
Rh Rh H + PPh3
Ph3P H Ph3P
Cl Cl
16
WC in alkene Hydrogenation: Catalytic Steps
(3) Ligand Association
H H CH
Ph3P H H2
Ph3P CH2 Ph3P Rh
Rh H + Rh CH2
PPh3
Ph3P CH2 Ph3P Cl H
Cl
H2CCl CH2
(4) Migration/Insertion
H H CH2
Ph3P H CH
H 2
Ph3P Rh CH2
Cl Rh
CH2
PPh Ph3P
3
Ph3P H Rh H
H2CCl CH2 Ph3P
Cl 17
WC in alkene Hydrogenation: Catalytic Steps
H CH2 H CH2
CH2 CH2
Ph3P Ph3P PPh3
Rh H + PPh3 Rh
Ph3P Ph3P H
Cl Cl
18
WC in alkene Hydrogenation: Catalytic Steps
H CH2
CH2
Ph3P PPh3 Ph3P PPh3
Rh Rh
Ph3P H Ph3P + CH3 CH3
Cl
Cl
19
WC
IN
A
C
T
I
O
N
20
WC in alkene Hydrogenation: Additional Notes
Applications
21
Alkene Hydrogenation & Chirality & Nobel
22
Alkene Hydrogenation, Chirality & Nobel
Coordinatively unsaturated
27
Oxidative addition…
X-Y X
+ X-Y LnMn+2
LnMn
LnMn Y
Ph3P H
Cl
Ph3P Cl Ir
Ir + H2
Ph3P H
Ph3P CO CO
28
(c) Insertion or migration
Migration of alkyl and hydride ligands
R L R
L+ M CO M C
S O
LnM CR
O
S
L'
R L' LnM CR
LnM LnM CR
C O
O
O
R
C
LnM O
29
H CH
2
M M CH2CH3
CH2
30
(d) Nucleophilic attack
R R 2+ H R +
C
L3Pd L3Pd C C OH
OH2
C R R
H R
-
O
L5M - -
CO + OH L5M C OH L5M H
+
CO2
31
(e) Reductive elimination
Ph3P Cl
Cl Rh
Ph3P Me Ph3P CO
Rh
Ph3P COR +
CO RCOMe
32