Ligand Exchange Processes on the Solvated Zinc Cation II. [Zn(H2O)4L]2+·2H2O with L = NH3, NH2(CH3), NH(CH3)2, and N(CH3)3

Abstract

Water-exchange mechanisms for the complexes [Zn(H2O)4L]2+·2H2O, L = NH3, NH2CH3, NH(CH3)2, and N(CH3)3, have been studied by density functional theory calculations (B3LYP/6–311+G**). The water-exchange reactions follow an associative (A) pathway involving formation of a six-coordinate intermediate [Zn(H2O)5L]2+·H2O. Electronic and steric effects of the amine ligands influence the activation barrier and the stability of the six-coordinate intermediate.