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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 [CuI CuI (RSNO)2 ]2+ or dicopper (I,I) mono-S-nitrosothiol complex [CuI CuI (RSNO)]2+ , which readily release RSNO in 88-94 % yield. The S-nitrosation proceeds by a mixed-valence [CuII CuIII (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 [CuII CuIII (μ-O)(μ-NO)]2+ complex is als