| 19795870 |
Mullins CS, Grapperhaus CA, Frye BC, Wood LH, Hay AJ, Buchanan RM, Mashuta MS: Synthesis and sulfur oxygenation of a (N3S) Ni complex related to nickel-containing superoxide dismutase. Inorg Chem. 2009 Nov 2;48(21):9974-6.
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-carboxa mido] 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. |
81(1,1,1,1) |