Petroleum Chemistry, Vol.47, No.3, 167-175, 2007
Influence of components of the PdCl2(PPh3)(2)-PPh3-p-toluenesulfonic acid catalytic system on the rate of cyclohexene hydrocarbalkoxylation with m-cresol
Kinetic parameters were determined for the cyclohexene hydrocarbalkoxylation reaction catalyzed by the PdCl2 (PPh3)(2)-PPh3-p-toluenesulfonic acid (TSA) catalyst system in the presence of m-cresol. It was shown that the reaction is first order in cyclohexene and a fractional order in PdCl2(PPh3)(2) and m-cresol and that the dependences of the reaction rate on P-CO, TSA and PPh3 concentrations are nonmonotonic in character. The inhibitory effect of tosylate and chloride ions on the reaction was revealed. The results were rationalized in terms of a mechanism that involves hydride complexes of the cation type as intermediates. A rate equation for the reaction was derived in terms of the steady-state hypothesis to fit to experimental data.