Synthesis and sulfur oxygenation of a (N3S)Ni complex related to nickel-containing superoxide dismutase.

Abstract

A nickel(II) thiolate complex incorporating three N-donor types (amino, amido, and imidazole) has been synthesized and characterized. The (N(3)S)Ni complex, [N-{2-[(2-mercapto-2-methylpropyl)amino]ethyl}-1-methylimidazole-2-carboxamido]nickel(II) (1), is stable in the presence of O(2) but readily forms the sulfinato (RSO(2)(-)) derivative 2 upon the addition of H(2)O(2). Electrochemical investigations of 1 reveal an irreversible sulfur-based oxidation at +0.17 V vs Fc(+)/Fc (200 mV/s) that shifts to +0.81 V upon oxidation to 2. Density functional theory investigations of 1 reveal a highest occupied molecular orbital that is predominantly sulfur-based, consistent with the observed sulfur-based oxidation and O(2) stability.

DOI: 10.1021/ic901246w

Cite this paper

@article{Mullins2009SynthesisAS, title={Synthesis and sulfur oxygenation of a (N3S)Ni complex related to nickel-containing superoxide dismutase.}, author={Christopher S. Mullins and Craig A Grapperhaus and Brian C Frye and Larry H Wood and Amy J Hay and Robert M. Buchanan and Mark S. Mashuta}, journal={Inorganic chemistry}, year={2009}, volume={48 21}, pages={9974-6} }