Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
68045 | Journal of Molecular Catalysis A: Chemical | 2007 | 9 Pages |
A kinetic study of the homogeneous hydroformylation of 1-hexene to the corresponding aldehydes (heptanal and 2-methyl-hexanal) was carried out using a rhodium catalyst formed by addition of 1 equiv. of 1,2-bis(diphenylphosphino)ethane (dppe) to Rh(acac)(CO)2 under mild reaction conditions (80 °C, 1–7 atm H2 and 1–7 atm CO) in toluene; in all cases linear to branched ratios were close to 2. The reaction rate is first-order in dissolved hydrogen concentration at pressures below 3 atm, but independent of this parameter at higher pressures. In both regimes (low and high H2 pressure), the initial rate was first-order with respect to the concentration of Rh and fractional order with respect to 1-hexene concentration. Increasing CO pressure had a positive effect on the rate up to a threshold value above which inhibition of the reaction was observed; the range of positive order on CO concentration is smaller when the total pressure is increased. The kinetic data and related coordination chemistry are consistent with a mechanism involving RhH(CO)(dppe) as the active species initiating the cycle, hydrogenolysis of the acyl intermediate as the rate-determining step of the catalytic cycle at low hydrogen pressure, and migratory insertion of the olefin into the metal-hydride bond as rate limiting at high hydrogen pressure. This catalytic cycle is similar to the one commonly accepted for RhH(CO)(PPh3)3 but different from previous proposals for Rh-diphosphine catalysts.
Graphical abstractThe kinetics and mechanism of 1-hexene hydroformylation were studied using Rh(acac)(CO)2/dppe as catalyst at 80 °C, 1–7 atm H2 and 1–7 atm CO in toluene. RhH(CO)(dppe) is the active species, hydrogenolysis of the acyl intermediate is rate-determining at low H2 pressure, while olefin insertion into the Rh-H bond is rate-limiting at high H2 pressure.Figure optionsDownload full-size imageDownload as PowerPoint slide