合成及含硫氧（N3S）镍配合物与含镍超氧化物歧化酶的关系。

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

机构信息

Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA.

出版信息

Inorg Chem. 2009 Nov 2;48(21):9974-6. doi: 10.1021/ic901246w.

PMID:19795870

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.

摘要

已合成并表征了一种包含三种 N-供体类型（氨基、酰胺基和咪唑基）的镍（II）硫醇配合物。（N(3)S）Ni 配合物，[N-{2-[(2-巯基-2-甲基丙基)氨基]乙基}-1-甲基咪唑-2-羧酰胺基]镍（II）（1），在存在 O(2)的情况下稳定，但在加入 H(2)O(2)时容易形成亚磺酸盐（RSO(2)(-))衍生物 2。对 1 的电化学研究表明，在 +0.17 V 相对于 Fc(+)/Fc（200 mV/s）处发生不可逆的基于硫的氧化，当氧化为 2 时，该氧化移至 +0.81 V。对 1 的密度泛函理论研究表明，最高占据分子轨道主要基于硫，与观察到的基于硫的氧化和 O(2)稳定性一致。