Redox-Neutral S-nitrosation Mediated by a Dicopper Center

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 [Cu^I Cu^I (RSNO)₂ ]²⁺ or dicopper (I,I) mono-S-nitrosothiol complex [Cu^I Cu^I (RSNO)]²⁺ , which readily release RSNO in 88-94 % yield. The S-nitrosation proceeds by a mixed-valence [Cu^II Cu^III (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 [Cu^II Cu^III (μ-O)(μ-NO)]²⁺ complex is also competent for O-nitrosation of MeOH. A rare [Cu^II Cu^II (μ-NO)(OMe)]²⁺ intermediate was isolated and fully characterized, suggesting the S-nitrosation may proceed through the intermediary of analogous [Cu^II Cu^II (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.