1. Hydroformylation (Oxo) Catalysis
Daniell B. Kelly
Department of Chemistry, Elmhurst College
BACKGROUND
Discovered by Otto Roelen in 1938
Cobalt catalysis dominated industrial hydroformylation until 1970’s  Rh
CO Dissociation
Uses:
Plastics
Detergents and surfactants
Solvents
Lubricants
Chemical Intermediates
18e-
HCo(CO)3
16e-
anti-Markovnikov
Hydride addition
Reductive
Elimination
18e-
18e-
Oxidative H2
Addition
1,2 Insertion
(reversing β elimination)
16e-
16e-
Alkyl migration
18e-
CO Add’n
d (aldehyde) dt
= k [alkene] [CO] [H2] [CO]-1
Rate:
Back reactions are prevented with increased CO pressure. As a result, the alkene isomerization and opportunity to make a branched alkyl is limited.