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 ΔG 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 K2[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···O and C–H···π hydrogen bonds.