Modelling proposed intermediates in the hydrocarbonylation of alkenes catalysed by rhodium complexes of PBui3 and PPri3.
In ethanol, hydrocarbonylation reactions of alkenes catalysed by triethylphosphine complexes of rhodium give alcohols as the products with low linear selectivity, whilst rhodium complexes of PPri3 or PBui3 give mainly aldehydes, again with low linear selectivity. Modelling the proposed acyl intermediates by studying [Rh(C(O)Me)(CO)m(L)4-m] (L = PPri3 or PBui3) shows that they exist as monophosphine species under the normal reaction conditions. In the absence of CO, [Rh(=C(OH)Me)(CO)L2]+ can also be formed. The implications of these NMR studies for the chemo- and regio-selectivity of the hydrocarbonylation reactions are discussed.
Cheliatsidou
Paraskevi
P
EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, Fife, UK KY16 9ST.
White
Daniel F S
DF
Slawin
Alexandra M Z
AM
Cole-Hamilton
David J
DJ