Electrochemical Synthesis of Cobalt Complexes with 4‐Methyl‐ N ‐(2‐pyridylmethyl)benzenesulfonamide (HL) − Crystal Structures of HL, [Co II L 2 ] and [Co III L 2 L o ] [L o = {HNC(CH 3 )} 2 C(CN)

Abstract

Electrochemical oxidation of cobalt in a solution of 4-methyl-N-(2-pyridylmethyl)benzenesulfonamide (HL, 1) in acetonitrile afforded the compounds [CoIIL2] (2) or [CoIIIL2Lo] (3). When 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) was added to the electrolytic phase, [CoIIL2bipy] (4) and [CoIIL2phen] (5) were obtained. The crystal structures of HL (1), [CoIIL2] (2) and [CoIIIL2Lo] (3) were determined by X-ray diffraction techniques. The compound [CoIIL2] is mononuclear and has a distorted tetrahedral [CoN4] geometry, with each amide ligand acting as an anionic (NamideNpy) bidentate ligand. In the monomeric complex [CoIIIL2Lo] the cobalt atom is in a distorted octahedral [CoN6] environment defined by the amide and pyridyl nitrogen atoms of two L− anionic ligands and the two nitrogen atoms of the NH groups of a new anionic ligand Lo, which is formed by trimerisation of three acetonitrile molecules in the electrolytic cell. The electronic, IR and FAB spectra of the compounds are discussed. (© Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)