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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:
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
OSTI Identifier:
1304729
Alternate Identifier(s):
OSTI ID: 1401002

Kundu, Subrata, Stieber, S. Chantal, Ferrier, Maryline Ghislaine, Kozimor, Stosh Anthony, Bertke, Jeffery A., and Warren, Timothy H.. Redox Non-Innocence of Nitrosobenzene at Nickel. United States: N. p., Web. doi:10.1002/anie.201605026.
Kundu, Subrata, Stieber, S. Chantal, Ferrier, Maryline Ghislaine, Kozimor, Stosh Anthony, Bertke, Jeffery A., & Warren, Timothy H.. Redox Non-Innocence of Nitrosobenzene at Nickel. United States. doi:10.1002/anie.201605026.
Kundu, Subrata, Stieber, S. Chantal, Ferrier, Maryline Ghislaine, Kozimor, Stosh Anthony, Bertke, Jeffery A., and Warren, Timothy H.. 2016. "Redox Non-Innocence of Nitrosobenzene at Nickel". United States. doi:10.1002/anie.201605026. https://www.osti.gov/servlets/purl/1304729.
@article{osti_1304729,
title = {Redox Non-Innocence of Nitrosobenzene at Nickel},
author = {Kundu, Subrata and Stieber, S. Chantal and Ferrier, Maryline Ghislaine and Kozimor, Stosh Anthony and Bertke, Jeffery A. and Warren, Timothy H.},
abstractNote = {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 [iPr2NNF6]Ni results in reduction of the PhNO ligand to a (PhNO)./ ⁻ species coordinated to a square planar NiII center in [iPr2NNF6]Ni(η2- ONPh). Ligand centered reduction leads to the (PhNO)-2 moiety bound to NiII supported by XAS studies. Ultimately, 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.},
doi = {10.1002/anie.201605026},
journal = {Angewandte Chemie (International Edition)},
number = 35,
volume = 55,
place = {United States},
year = {2016},
month = {8}
}