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

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Treatment of a dicopper(I,I) complex with nitric oxide produces a dicopper μ-oxo, μ-nitrosyl complex [ L Cu 2 (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 [ L Cu II Cu I ] 3+ synthon. Full characterization of the thermal-sensitive [ L Cu 2 (μ-O)(μ-NO)] 2+ complex with IR, EPR, and X-ray crystallography suggests a localized mixed-valent Cu III, Cu II, O 2–, NO – formulation. The [Cu 2 (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 [Cu 2 (μ-O)(μ-NO)] 2+ core is potentially relevant to anaerobic methane oxidation observed in methanotrophic archaea.