Syntheses, crystal structure and theoretical investigation of novel heteroleptic complexes of nickel(II) with N-R-sulfonyldithiocarbimate and phosphine ligands

摘要

Five new complexes of general formula: [Ni(RSO_2NCS _2)(dppe)], where R = C_6H_5 (1), 4-ClC _6H_4 (2), 4-BrC_6H_4 (3), 4-IC _6H_4 (4) and dppe = 1,2-bis(diphenylphosphino)ethane and [Ni(4-IC_6H_4SO_2NCS_2)(PPh _3)_2] (5), where PPh_3 = triphenylphosphine, were obtained in crystalline form by the reaction of the appropriate potassium N-R-sulfonyldithiocarbimate K_2(RSO_2NCS_2) and dppe or PPh_3 with nickel(II) chloride in ethanol/water. The elemental analyses and the IR, 1H NMR, 13C NMR and 31P NMR spectra are consistent with the formation of the square planar nickel(II) complexes with mixed ligands. All complexes were also characterized by X-ray diffraction techniques and present a distorted cis-NiS_2P_2 square-planar configuration around the Ni atom. Quantum chemical calculations reproduced the crystallographic structures and are in accord with the spectroscopic data. Rare C-H?Ni intramolecular short contact interactions were observed in the complexes 1-5.