Dicopper μ-Oxo, μ-Nitrosyl Complex from the Activation of NO or Nitrite at a Dicopper Center.

Treatment of a dicopper(I,I) complex with nitric oxide produces a dicopper μ-oxo, μ-nitrosyl complex [LCu2(μ-O)(μ-NO)]2+, representing the first structurally characterized μ-oxo, μ-nitrosyl metal complex. This compound can also be synthesized from the reaction of nitrite with an [LCuIICuI]3+ synthon. Full characterization of the thermal-sensitive [LCu2(μ-O)(μ-NO)]2+ complex with IR, EPR, and X-ray crystallography suggests a localized mixed-valent CuIII, CuII, O2-, NO- formulation. The [Cu2(μ-O)(μ-NO)]2+ core efficiently oxidizes exogenous substrates, such as phosphine, cyclohexadienes, and isochroman to afford phosphine oxide, benzene, and 1-isochromanone. Since both nitrite and nitric oxide are proposed oxidants in denitrifying methane oxidation, the oxidative reactivity of [Cu2(μ-O)(μ-NO)]2+ core is potentially relevant to anaerobic methane oxidation observed in methanotrophic archaea.