Kinetic aspects of the influence of CO pressure on cyclohexene hydrocarbomethoxylation catalyzed by a diphosphine palladium system. Thermodynamic characteristics of some ligand exchange reactions

Kinetic models of the cyclohexene hydromethoxycarbonylation catalyzed by the Pd(OAc)2/trans‐2,3‐bis(diphenylphosphinomethyl)norbornane/p‐toluensulfonic acid

“…Earlier in the temperature range 358–383 K in the region of initial rates, we established the first orders of this reaction by cyclohexene and Pd(OAc) 2 concentrations . We also detected extreme dependence of the initial rate on CO pressure and TBDPN concentration and nonlinear growth of the rate with increasing of the methanol concentration at the initial stage of hydromethoxycarbonylation . The interpretation of the established patterns was given on the basis of generally accepted hydride mechanism, and the equation of the initial reaction rate was obtained .…”

“…Nevertheless, to develop industrially important processes, it is necessary to study kinetics throughout the entire reaction to deep conversions. In this connection, we have continued our earlier research of the model reaction of cyclohexene hydromethoxycarbonylation catalyzed by the Pd(OAc) 2 / trans ‐2,3‐bis (diphenylphosphinomethyl) norbornane (TBDPN)/ p ‐toluensulfonic acid (TsOH) system (Scheme ).…”

“…We have entirely described the methods of kinetic experiment and reaction mixture analysis in Refs. .…”

“…On the basis of this mechanism, we obtained the equation of the initial reaction rate and estimated its effective constants under the conditions of one‐factor experiments on the various reaction participants: …”

“…The effective constants of this equation in the studied temperature range were estimated, and the effective activation energies were calculated on the basis of the Arrhenius equation. A comparison of the values of these energies allowed us to estimate the relative stability of some catalytically inactive palladium species in hydromethoxycarbonylation …”