title: Redox Non-Innocence of Nitrosobenzene at Nickel.
abstract: Nitrosobenzene (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 [(i) Pr2 NNF6 ]Ni results in reduction of the PhNO ligand to a (PhNO)(./-) species coordinated to a square planar Ni(II) center in [(i) Pr2 NNF6 ]Ni(η(2) -ONPh). Ligand centered reduction leads to the (PhNO)(2-) moiety bound to Ni(II) 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.
authors.affiliation: Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA. skundu.chem@gmail.com.
authors.forename: Subrata
authors.identifier: 0000-0002-3533-3206
authors.initials: S
authors.lastname: Kundu
authors.affiliation: Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, 87545, USA. sestieber@cpp.edu.|Department of Chemistry and Biochemistry, California State Polytechnic University, Pomona, CA, 91768, USA. sestieber@cpp.edu.
authors.forename: S Chantal E
authors.initials: SC
authors.lastname: Stieber
authors.affiliation: Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, 87545, USA.
authors.forename: Maryline G
authors.initials: MG
authors.lastname: Ferrier
authors.affiliation: Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, 87545, USA.
authors.forename: Stosh A
authors.initials: SA
authors.lastname: Kozimor
authors.affiliation: Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA.
authors.forename: Jeffery A
authors.initials: JA
authors.lastname: Bertke
authors.affiliation: Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA. thw@georgetown.edu.
authors.forename: Timothy H
authors.identifier: 0000-0001-9217-8890
authors.initials: TH
authors.lastname: Warren
keywords: X-ray spectroscopy; nickel; nitric oxide; nitrosobenzene; redox-active ligands