Photochemical Hydroformylation of Olefins with Cobalt Catalysts. 1. Neutral Cobalt Carbonyls

Article abstract of DOI:10.1021/ja00415a029

The Co2(CO)8 and Co4(CO)12 catalyzed hydroformylation of octene-1 and cyclohexene in hydrocarbon solvents is strongly retarded by UV irradiation.In situ UV and IR spectroscopy reveals that the active catalyst HCo(CO)4 is decomposed via photochemically produced *Co(CO)4 radicals.Neither in the presence of carbon monoxide and hydrogen nor upon addition of HSi(OEt)3 does irradiation of Co2(CO)6(P(n-Bu)3)2 lead to the formation of HCo(CO)3P(n-Bu)3.Added octene-1 is isomerized to internal olefins under these conditions, but not hydroformylated.Seventeen-electron species of the type *Co(CO)3L (L = CO or P(n-Bu)3), produced by photolytic cleavage of the corresponding dimers, are obviously not able to activate molecular hydrogen or carbon monoxide nor to abstract hydrogen from methylcyclohexane or triethoxysilane.