Redox Non‐Innocence of Nitrosobenzene at Nickel

Abstract

AbstractNitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox‐active nitric oxide derivative. Capture of nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [iPr2NNF6]Ni results in reduction of the PhNO ligand to a (PhNO)./− species coordinated to a square planar NiII center in [iPr2NNF6]Ni(η2‐ONPh). Ligand centered reduction leads to the (PhNO)2− moiety bound to NiII supported by XAS studies. Systematic investigation of structure–reactivity patterns of (PhNO)./− and (PhNO)2− ligands reveals parallels with superoxo (O2)./− and peroxo (O2)2− ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.