Journal of Organometallic Chemistry p. 205 - 214 (1984)
Update date:2022-08-11
Topics:
Mirbach, Marlis F.
High pressure IR and UV spectroscopic experiments confirm the Heck and Breslow mechanism of the hydroformylation of 1-octene and cyclohexene with Co2(CO)8 as the starting catalyst.The major repeating unit is HCo(CO)4, which is formed via the reaction of acylcobalt tetracarbonyl with H2.The rates are 6.7 x 10-4 mol l-1 min-1 and 8.8 x 10-5 mol l-1 min-1 for 1-octene and cyclohexene, respectively at 80 deg C and 95 bar CO/H2 = 1 in methylcyclohexane.The alternative reaction of RCOCo(CO)4 with HCo(CO)4 is only a minor pathway, with rates of 1.8 x 10-5 mol l-1 min-1 and 1.1 x 10-5 mol l-1 min-1 for 1-octene and cyclohexene, respectively.It represents an exit from the catalytic cycle.The activation of the catalyst precursor Co2(CO)8 is the slowest step of the reaction.
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