Redox Non-Innocence of Nitrosobenzene at Nickel

Subrata Kundu; S Chantal E Stieber; Maryline G Ferrier; Stosh A Kozimor; Jeffery A Bertke; Timothy H Warren

doi:10.1002/anie.201605026

Redox Non-Innocence of Nitrosobenzene at Nickel

Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10321-5. doi: 10.1002/anie.201605026. Epub 2016 Jul 29.

Authors

Subrata Kundu¹, S Chantal E Stieber^{2

3}, Maryline G Ferrier⁴, Stosh A Kozimor⁴, Jeffery A Bertke⁵, Timothy H Warren⁶

Affiliations

¹ Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA. skundu.chem@gmail.com.
² Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, 87545, USA. sestieber@cpp.edu.
³ Department of Chemistry and Biochemistry, California State Polytechnic University, Pomona, CA, 91768, USA. sestieber@cpp.edu.
⁴ Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, 87545, USA.
⁵ Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA.
⁶ Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA. thw@georgetown.edu.

PMID: 27471147
DOI: 10.1002/anie.201605026

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.

Keywords: X-ray spectroscopy; nickel; nitric oxide; nitrosobenzene; redox-active ligands.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.