Theoretical study of hydrolysis of an imine oxime in aqueous solution and crystal structure and spectroscopic characterization of a platinum(II) complex containing the hydrolysis product

Abstract

The hydrolysis of an imine oxime (ppeieoH) in neutral and acidic aqueous solutions was studied using DFT at the B3LYP/6-311G(d,p) level. The rate-determining step at the neutral and acidic aqueous solutions is the nucleophilic attack of the water molecules to the neutral or protonated imine C atom of ppeieoH. The activation energy is much lower in the acidic hydrolysis. The hydrolysis of ppeieoH results in the parent carbonyl oxime (inapH) and amine compounds with Delta G (cal) values of 8.66 and 11.02 kJ mol(-1) in the neutral and acidic solutions, respectively. The hydrolysis of ppeieoH was observed experimentally during its reaction with K-2[PtCl4] in an aqueous solution. The reaction yielded [PtCl(inap)(DMSO)], which contains only the hydrolysis product inap. The new platinum(II) complex was characterized spectroscopic techniques and X-ray diffraction. The platinum(II) ion is coordinated by chlorido, carbonyl oxime (inap), and DMSO ligands forming a distorted square-planar arrangement. The molecules of the platinum(II) complex were connected by weak non-conventional C-H center dot center dot center dot O and C-H center dot center dot center dot pi hydrogen bonds.