一个 S-亚硝酰硫醇还原裂解得到的铜（II）硫醇盐。

A copper(II) thiolate from reductive cleavage of an S-nitrosothiol.

机构信息

Department of Chemistry, Georgetown University, Box 571227-1227, Washington, D.C. 20057, USA.

出版信息

Inorg Chem. 2012 Aug 20;51(16):8658-60. doi: 10.1021/ic301356h. Epub 2012 Aug 7.

Abstract

S-Nitrosothiols RSNO represent circulating reservoirs of nitric oxide activity in the plasma and play intricate roles in protein function control in health and disease. While nitric oxide has been shown to reductively nitrosylate copper(II) centers to form copper(I) complexes and ENO species (E = R(2)N, RO), well-characterized examples of the reverse reaction are rare. Employing the copper(I) β-diketiminate [Me(2)NN]Cu, we illustrate a clear example in which an RS-NO bond is cleaved to release NO(gas) with formation of a discrete copper(II) thiolate. The addition of Ph(3)CSNO to [Me(2)NN]Cu generates the three-coordinate copper(II) thiolate [Me(2)NN]CuSCPh(3), which is unstable toward free NO.

摘要

S-亚硝基硫醇 RSNO 代表血浆中一氧化氮活性的循环储库，并在健康和疾病中的蛋白质功能控制中发挥复杂作用。虽然已经表明一氧化氮将亚硝基化铜 (II) 中心还原为形成铜 (I) 配合物和 ENO 物种 (E = R(2)N, RO)，但很少有特征明确的逆反应的例子。利用铜 (I) β-二酮腙 [Me(2)NN]Cu，我们说明了一个明显的例子，其中 RS-NO 键被切断，释放出 NO(gas)，同时形成离散的铜 (II) 硫醇盐。Ph(3)CSNO 与 [Me(2)NN]Cu 的加成生成三配位铜 (II) 硫醇盐 [Me(2)NN]CuSCPh(3)，其对游离 NO 不稳定。