New synthetic routes to a disulfidodinickel(II) complex: Characterization and reactivity of a Ni2(μ-η2:η2- S2) core

Abstract

Activation of elemental sulfur by the monovalent nickel complex [PhTt tBu]Ni(CO) [PhTttBu = phenyl{tris[(tert-butylmethyl)thio] methyl}borate] generates the disulfidodinickel(II) complex 2. This species is alternatively accessible via thermal decomposition of [PhTttBu] Ni(SCPh3). Spectroscopic, magnetic, and X-ray diffraction studies establish that 2 contains a μ-η2:η2-S 2 ligand that fosters antiferromagnetic exchange coupling between the NiII ions. This observation is in contrast to the lighter congener, oxygen, which strongly favors the bis(μ-oxo)dinickel(III) structure. 2 oxidizes PPh3 to SPPh3 and reacts with O2, generating several products, one of which has been identified as [(PhTt tBu)Ni]2(μ-S) (3). © 2008 American Chemical Society.