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Title: Redox Non‐Innocence of Nitrosobenzene at Nickel

Journal Article · · Angewandte Chemie
ORCiD logo [1];  [2];  [3];  [3];  [1]; ORCiD logo [1]
  1. Department of Chemistry Georgetown University Box 571227 Washington DC 20057-1227 USA
  2. Inorganic, Isotope and Actinide Chemistry, Los Alamos National Laboratory Los Alamos NM 87545 USA, Department of Chemistry and Biochemistry California State Polytechnic University Pomona CA 91768 USA
  3. Inorganic, Isotope and Actinide Chemistry, Los Alamos National Laboratory Los Alamos NM 87545 USA
+ Show Author Affiliations

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 Pr 2 NN F6 ]Ni results in reduction of the PhNO ligand to a (PhNO) ./− species coordinated to a square planar Ni II center in [ i Pr 2 NN F6 ]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 (O 2 ) ./− and peroxo (O 2 ) 2− ligands, respectively, and forecasts reactivity patterns of the more transient HNO ligand.

Sponsoring Organization:
USDOE
OSTI ID:
1401870
Journal Information:
Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 35 Vol. 128; ISSN 0044-8249
Publisher:
Wiley Blackwell (John Wiley & Sons)Copyright Statement
Country of Publication:
Germany
Language:
English

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