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Abstract A redox‐neutralS‐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^ICu^I(RSNO)₂]²⁺or dicopper (I,I) mono‐S‐nitrosothiol complex [Cu^ICu^I(RSNO)]²⁺, which readily release RSNO in 88–94 % yield. TheS‐nitrosation proceeds by a mixed‐valence [Cu^IICu^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^IICu^III(μ‐O)(μ‐NO)]²⁺complex is also competent forO‐nitrosation of MeOH. A rare [Cu^IICu^II(μ‐NO)(OMe)]²⁺intermediate was isolated and fully characterized, suggesting theS‐nitrosation may proceed through the intermediary of analogous [Cu^IICu^II(μ‐NO)(SR)]²⁺species. This redox‐ and proton‐neutralS‐nitrosation process is the first functional model of ceruloplasmin in mediatingS‐nitrosation of external thiols, with implications for biological copper sites in the interconversion of NO^./RSNO.