Abstract
The kinetics of the reaction of cis-[PdCl 2(CN- p-C 6H 4Cl)(PPh 3)] with N-methylaniline yielding the carbene derivative cis-[PdCl 2 {C(NH- p-C 6H 4Cl)NMePh} (PPh 3)] have been studied in various solvents such as acetone, 1, 4-dioxane, 1,2-dichloroethane, and benzene. Overall rates for the stepwise process increase with decreasing ability of the solvent to form hydrogen bonds with the attacking amine. A kinetic study is also reported for the reactions of N-methylaniline with cis- [PdCl 2(CN- p-C 6H 4Me)(L)] in 1,2-dichloroethane (L = P(OMe) 3, P(OMe) 2Ph, PPh 3. PMePh 2, PMe 2Ph, PEt 3, PCy 3). The cis ligand L affects reaction rates through both steric and electronic factors. The nucleophilic attack of the amine on the CN carbon atom of coordinated isocyanide is favoured by low steric requirements and high π-acceptor ability of L. The activation parameters for the bimolecular nucleophilic attack when L = PPh 3 are △H ≠ 2 = 9.8 ± 0.7 kcal/mol and △S ≠ 2 = — 30 ± 2 e.u.
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