O,O′-Dimethyl diphenyldithiophosphates of nickel(II) with N-donor ligands

Abstract

The present work demonstrates the synthesis and characterization of donor stabilized addition complexes of nickel(II) with O,O′-dimethyl diphenyldithiophosphates [[(ArO)2PS2]2NiL2] (Ar = 2,4-(CH3)2C6H3, 3,4-(CH3)2C6H3, and 3,5-(CH3)2C6H3; L = pyridine, 4-ethylpyridine, and 3,4-dimethylpyridine). These complexes were successfully isolated and structurally characterized by single crystal X-ray analysis. The complexes [[(2,4-CH3)2C6H3O]2PS2]2Ni(C5H5N), [[(2,4-CH3)2C6H3O]2PS2]2Ni[4-(C2H5)C5H4N]2, and [[(3,4-CH3)2C6H3O]2PS2]2Ni(C5H5N)2 were crystallized in the monoclinic crystal system with space group P21/n, whereas the complex [[(3,5-CH3)2C6H3O]2PS2]2Ni[3,4-(CH3)2C5H3N]2 was crystallized in the monoclinic crystal system with different space group P21/c. X-ray diffraction analysis of complexes reveals a six-coordinated octahedral geometry for the NiS4N2 chromophore, defined by two chelating diphenyldithiophosphate anions as well as two N-donor ligands. Two diphenyldithiophosphate ligands are coordinated to the nickel ion as a bidentate chelating via the two thiolate S atoms, forming a four-membered chelate ring in the equatorial plane. The N atoms from two donor ligands are axially coordinated to the Ni atom in trans position.