title: A copper(II) thiolate from reductive cleavage of an S-nitrosothiol.
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.
authors.affiliation: Department of Chemistry, Georgetown University, Box 571227-1227, Washington, D.C. 20057, USA.
authors.forename: Marie M
authors.initials: MM
authors.lastname: Melzer
authors.forename: Susanne
authors.initials: S
authors.lastname: Mossin
authors.forename: Allan Jay P
authors.initials: AJ
authors.lastname: Cardenas
authors.forename: Kamille D
authors.initials: KD
authors.lastname: Williams
authors.forename: Shiyu
authors.initials: S
authors.lastname: Zhang
authors.forename: Karsten
authors.initials: K
authors.lastname: Meyer
authors.forename: Timothy H
authors.initials: TH
authors.lastname: Warren
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D015394:Molecular Structure; D009569:Nitric Oxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D026403:S-Nitrosothiols / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D056831:Coordination Complexes; D026403:S-Nitrosothiols; D013438:Sulfhydryl Compounds; D009569:Nitric Oxide; D003300:Copper