Redox Non‐Innocence of Nitrosobenzene at Nickel

• DOI: 10.1002/anie.201605026
• Publication Date: 2016-08-03T08:17:42Z
• Authors: Subrata Kundu; S. Chantal E. Sti...; Maryline G. Ferrier; Stosh A. Kozimor; Jeffery A. Bertke; Timothy H. Warren
• Keywords: Nitrosobenzene; Nitroxyl; Reactivity; Moiety

Abstract Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), biologically relevant, redox‐active nitric oxide derivative. Capture nitrosobenzene at the electron‐deficient β‐diketiminato nickel(I) complex [ i Pr 2 NN F6 ]Ni results in reduction PhNO ligand to ./− species coordinated square planar Ni II center ]Ni(η ‐ONPh). Ligand centered leads 2− moiety bound supported by XAS studies. Systematic investigation structure–reactivity patterns and ligands reveals parallels with superoxo (O ) peroxo ligands, respectively, forecasts reactivity more transient HNO ligand.