On the mechanism of the Co2(CO)8 catalyzed hydroformylation of olefins in hydrocarbon solvents. A high pressure UV and IR study |
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Authors: | Marlis F. Mirbach |
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Affiliation: | Universität Duisburg, F.B.6 Chemie, Lotharstrasse 63, D-4100 Duisburg F.R.G. |
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Abstract: | 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 × 10?4 mol l?1 min?1 and 8.8 × 10?5 mol l?1 min?1 for 1-octene and cyclohexene, respectively at 80°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 × 10?5 mol l?1 min?1 and 1.1 × 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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