Unprecedented N-inserted disulfide ligand stabilized by coordination to the electropositive Co-III center

Abstract

The reaction of Co-II and 2,2'-dipyridyldisulfide (PySSPy) in the presence of azide produced a peculiar monomeric complex [Co-III(PyS)(PyS-N-SPy)(N-3)] (1). In this reaction, redox chemistry takes place, which is associated mainly with the oxidation of Co-II to Co-III and the reduction of PySSPy. During the reaction, the azide ion decomposes and donates a nitrogen atom to PySSPy. The crystal structure of 1 provides evidence that the unusual, N-inserted ligand PyS-N-SPy can be stabilized through coordination to the electropositive Co-III ion. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).