Abstract
Cobalt-catalyzed hydroformylation of olefins was found to proceed even at ambient temperature under UV irradiation in the presence of phosphine. Extremely high selectivity toward straight-chain aldehyde (99% in case of 1-hexene) was obtained by lowering the partial pressure of carbon monoxide at ambient temperature. A catalytic species different from the well-known species under high pressure of carbon monoxide and high temperature contributed to the highly selective formation of straight-chain aldehydes. Two photochemical processes were suggested to be involved in the photochemical hydroformylation reaction, that is, the formation of HCo(CO)3PBu3 from the cationic cobalt species, [Co(CO)3(PBu3)2]+, and then the formation of the coordinatively unsaturated hydride, HCo(CO)2PBu3.
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