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Transition Metal Catalysis
Transition Metal Catalysis
Transition Metal Catalysis
Addition to Alkene
Topic
Cycle
Hydrogenation
Catalyst
RhCl(PPh3)
H2C=CH2 + H2 H3C-CH3
Wilkinsons Catalyst
Hydrosilation
H2PtCl6
Ni(P[O(o-tolyl)]3
Hydrocyanation
H2C=CH2 + HCN H3C-CH2CN
Notes
Hydroformylation
HCo(CO)4 / HRh(PPh3)2(CO)
H2C=CH2 + CO + H2 H3C-CH2CHO
Carbonylation
Reppe / BASF
Monsanto
Cobalt-based
Rhodium-based
Iridium-based
BP Cativa
[RhI2CO2]
Polyketone Formation
[PdL2(OR)]+
Grignard
Coupling Reactions
RMgX
Negishi
Ni(acac)2 / (dppe)NiCl2 /
FeCl3 / CoCl2 / CrCl2
(Ph3P)4Ni / (Ph3P)2PdCl2
RZnX
Stille
Pd(dba)3
RSnR3
(MeCN)2PdCl2
Mizoroki-Heck
PdLn
H2C=CHR
Pd(0) or Pd(II)
Fisher
M=CH2X
R = Hydrogen or Carbon
Alkylidene
R2C:
Sonogashira
Cu-CC-R
X = Heteroatom
Schrock
Carbenes
Nucleophillic
M=CH2R
Free carbene
Alkene Polymerisation
Metathesis
Schrocks
Mo(=CHCMe2Ph)(=NAr)(-OR)2
Grubbs
RuCl2(PCy3)2(=CHPh)
RuCl2(PCy3)(:C(NR2)2)(=CHPh)
RuCl2(NR2)2(:C(NR2)2)(=CHPh)
Ziegler
TiCl4
Metallocene
MCl2(Cp)2
Highly active
React with hindered alkenes
Control reactivity by altering
alkoxide groups
Poor functional group
tolerance
Undergo the Chauvin
mechanism
Activated by AlEt3
Mild conditions
Controlled process yields
isotatic, high density
Undergoes Cossee-Arlman
Mechanism
Weak co-catalyst to pull off Cl
Co-catalyst: AlClR2
MCl2(Cp)2
Co-catalyst: MAO
MR2(Cp)2
Co-catalyst: [CPh3][B(C6F5)4]