Mechanism of the solvent effect on the rate of the cyclohexene hydroxymethoxycarbonylation catalyzed by bis(triphenylphosphine)palladium |
| |
| Authors: | A I Ermakov V A Averyanov E M Kazakov N T Sevost’yanova |
| |
| Institution: | 1.Novomoskovskyi Institute of Mendeleev Russian Chemical Engineering University,Novomoskovsk, Tul’skaya oblast,Russia;2.Tolstoi Tula State Pedagogical University,Tula,Russia;3.Tula State University,Tula,Russia |
| |
| Abstract: | Kinetic data of the cyclohexene hydroxymethoxycarbonylation catalyzed by bis(triphenylphosphine) palladium Pd(PPh3)2 were processed and considered on the basis of the quantum-chemical calculations. By the method of density functional DFT
PBE/3z we found that among the possible catalyst moleculs based on the tetrakis(triphenylphosphine)palladium the most stable
is Pd(PPh3)2 with the coordination number of palladium equal 2. The interaction energy of Pd(PPh3)2 with acetone, acetonitrile, dichloroethane, 1,4-dioxane, nitromethane, and tetrahydrofuran calculated by PM3 method was found
to correlate linearly with the reaction rate logarithm. The mechanism of the solvent effect on the reaction rate consists
in a specific complexation with the catalyst depending on the molecule rigidity and the creation of energetic and steric constraints
for the substrate to access the catalyst. |
| |
| Keywords: | |
| 本文献已被 SpringerLink 等数据库收录！ |
|
