Infrared spectroelectrochemical studies of bis(1,2-dithiolene) complexes of transition metals

Abstract

Infrared spectroelectrochemical studies have been conducted on the series of complexes [M(mnt)2]n- (mnt = cis-1,2-dicyanoethylene-1,2-dithiolate; M = Fe or Au, n = 1; M = Co, Ni, Cu, Pd or Pt, n = 2). The v(CN) values for related mono-, di-, and (for M = Cu or Au) tri-anions indicate that the extent of the metal contribution to the π orbital, which is delocalised over the mnt ligands, is directly comparable to that for the tri- and tetra-anionic forms of related tris(mnt) complexes, [M(mnt)3]n- (n = 3 or 4). Previous ESR-based assignments of the singly occupied molecular orbital for [M(mnt)2]2-, M = Cu or Au, to predominantly metal (Cu)- or ligand (Au)-based orbitals are supported by the tre..