Synthesis, structure, redox properties and reactivity of a copper(II) complex with a bidentate (N,S) chelate ligand

The complex [CuL2(OClO3)(2)] [L=2-(benzylthio)aniline] has been synthesised and its crystal structure determined. It displays a one-electron reductive response at -0.38 V versus SCE and its reactions with N-3(-) and SCN- ions give [CuL2(N-3)(2)] and [CuL2(SCN)(2)]. The copper atom in [CuL2(OClO3)(2)] assumes a tetragonally distorted, octahedral geometry with two semicoordinated perchlorate oxygens in the axial positions. Two perchlorate ions are also linked to the amino nitrogen of other molecules by intermolecular hydrogen bonding. A plausible description of redox orbitals is given on the basis of single point density functional theory calculations.