| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 40757 | Applied Catalysis A: General | 2012 | 8 Pages |
The reactants and components of a catalytic system were studied for their effects on the rate of Pd-catalysed cyclohexene hydrocarbomethoxylation. First-order reaction rate dependences were established for cyclohexene and Pd(OAc)2, while non-monotonic rate dependences were determined for the diphosphine and p-toluenesulphonic acid concentrations and the СО pressure. The reaction was shown to follow first-order kinetics when the methanol concentration was below 0.4 mol/L; however, the reaction rate slowed upon a further increase in the methanol concentration. The obtained results were interpreted by considering a hydride mechanism supplemented with ligand exchange reactions, which decreased the activity of the catalyst, and with hydride complex annihilations by p-toluenesulphonic acid, resulting in complete loss of catalytic activity. Treatment of the proposed mechanism using the quasi-equilibrium concentration method gave a kinetic equation for the reaction that was consistent with the experimental data.
Graphical abstractFigure optionsDownload full-size imageDownload high-quality image (110 K)Download as PowerPoint slideHighlights► Novel kinetic study of Pd-catalysed cyclohexene hydrocarbomethoxylation. ► High-performing trans-2,3-bis(diphenylphosphinomethyl)norbornane used as a catalyst. ► Influence of reactants and catalyst component concentrations were revealed.
