Redox‐Neutral S‐nitrosation Mediated by a Dicopper Center

Abstract

A redox‐neutral S‐nitrosation of thiol has been achieved at a dicopper(I,I) center. Treatment of dicopper (I,I) complex with excess NO. and thiol generates a dicopper (I,I) di‐S‐nitrosothiol complex [CuICuI(RSNO)2]2+ or dicopper (I,I) mono‐S‐nitrosothiol complex [CuICuI(RSNO)]2+, which readily release RSNO in 88–94 % yield. The S‐nitrosation proceeds by a mixed‐valence [CuIICuIII(μ‐O)(μ‐NO)]2+ species, which deprotonates RS‐H at the basic μ‐O site and nitrosates RS− at the μ‐NO site. The [CuIICuIII(μ‐O)(μ‐NO)]2+ complex is also competent for O‐nitrosation of MeOH. A rare [CuIICuII(μ‐NO)(OMe)]2+ intermediate was isolated and fully characterized, suggesting the S‐nitrosation may proceed through the intermediary of analogous [CuIICuII(μ‐NO)(SR)]2+ species. This redox‐ and proton‐neutral S‐nitrosation process is the first functional model of ceruloplasmin in mediating S‐nitrosation of external thiols, with implications for biological copper sites in the interconversion of NO./RSNO.