Syntheses, crystal structure and spectroscopic characterization of novel N-R-sulfonyldithiocarbimate and triphenylphosphine nickel(II) complexes.

Abstract

Three new complexes of the general formula: [Ni(PPh3)2(RSO2N_/CS2)] where R_/2-CH3C6H4 (1), 4-CH3C6H4 (2) and 4-BrC6H4 (3) were obtained in crystalline form by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimates (K2(RSO2N_/CS2)) and triphenylphosphine with nickel(II) chloride in ethanol_/water. The 1 complex crystallizes in the centrosymmetric space group of the triclinic system with two molecules per unit cell, while 2 and 3 complexes crystallize in the Pbca space group of the orthorhombic system with eight molecules per unit cell. The X-ray single-crystal analysis showed that all complexes present a similarly distorted square-planar configuration around the nickel atom due to the steric effect of the triphenylphosphine ligands and the didendate chelation by the two sulfur atoms of the dithiocarbimate ligand. The IR and UV_/Vis spectral data are consistent with the formation of almost square-planar nickel complexes. The 1H NMR, 13C NMR, 31P NMR spectra showed the expected signals for the triphenylphosphine and the dithiocarbimate moieties.