skip to main content

Title: Redox Non-Innocence of Nitrosobenzene at Nickel

Nitrosobenzene (PhNO) serves as a stable analogue of nitroxyl (HNO), a biologically relevant, redox-active nitric oxide derivative. Capture of nitrosobenzene at the electrondeficient β-diketiminato nickel(I) complex [ iPr 2NN F6]Ni results in reduction of the PhNO ligand to a (PhNO) ./ ⁻ species coordinated to a square planar Ni II center in [ iPr 2NN F6]Ni(η 2- ONPh). Ligand centered reduction leads to the (PhNO) -2 moiety bound to Ni II supported by XAS studies. Ultimately, 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.
Authors:
ORCiD logo [1] ;  [2] ;  [3] ;  [3] ;  [1] ; ORCiD logo [1]
  1. Georgetown Univ., Washington, DC (United States). Dept. of Chemistry
  2. Los Alamos National Lab. (LANL), Los Alamos, NM (United States); California State Polytechnic Univ., Pomona, CA (United States). Dept. of Chemistry and Biochemistry
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
OSTI Identifier:
1304729
Report Number(s):
LA-UR-16-23579
Journal ID: ISSN 1433-7851
Grant/Contract Number:
AC52-06NA25396; AC02-76SF00515; CHE-1459090; CHE-1337975
Type:
Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Name: Angewandte Chemie (International Edition); Journal Volume: 55; Journal Issue: 35; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Research Org:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF); USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry