Reductive NO Coupling at Dicopper Center via a [Cu₂(NO)₂]²⁺ Diamond-Core Intermediate

Abstract

Treatment of a dicopper(I,I) complex with excess amounts of NO leads to the formation of a dicopper dinitrosyl [Cu₂(NO)₂]²⁺ complex capable of (i) releasing two equivalents of NO reversibly in 90% yield and (ii) reacting with another equivalent of NO to afford N₂O and dicopper nitrosyl oxo species [Cu₂(NO)(O)]²⁺. Resonance Raman characterization of the [Cu₂(NO)₂]²⁺ complex shows a ¹⁵N-sensitive N═O stretch at 1527.6 cm^-1 and two Cu-N stretches at 390.6 and 414.1 cm^-1, supporting a symmetric diamond-core structure with bis-μ-NO ligands. The conversion of [Cu₂(NO)₂]²⁺ to [Cu₂(NO)O]²⁺ occurs via a rate-limiting reaction with NO and bypasses the dicopper oxo intermediate, a mechanism distinct from that of diFe-mediated NO reduction to N₂O.