Quantum chemical modeling of nucleophilic substitution reactions in the complexes cis-Pt(NH3)2Cl2 and cis-Pd(NH3)2Cl2

摘要

The B3LYP/6-31G~(**) method was used for the study of nucleophilic substitution reaction in platinum and palladium square-planar cis-diaminate complexes. The processes under consideration take place in two steps through pentacoordinated transition states. Activation barriers for both steps of these processes in gaseous phase and aqueous solution were calculated. A major role in the increase in the activation energies is played by the formation of the intermediate electrostatic Van der Waals' complexes. For the complex cis-[Pd(NH3)2Cl2], the activation barriers in the nucleophilic substitution reaction are considerably lower than those for the complex cis-[Pt(NH3)2Cl2].