Redox Non‐Innocence of Nitrosobenzene at Nickel |
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| Authors: | Dr. Subrata Kundu Prof. Dr. S. Chantal E. Stieber Dr. Maryline G. Ferrier Dr. Stosh A. Kozimor Dr. Jeffery A. Bertke Prof. Dr. Timothy H. Warren |
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| Affiliation: | 1. Department of Chemistry, Georgetown University, Washington, DC, USA;2. Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, USA;3. Department of Chemistry and Biochemistry, California State Polytechnic University, Pomona, CA, USA |
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| 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 [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. 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. |
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| Keywords: | nickel nitric oxide nitrosobenzene redox-active ligands X-ray spectroscopy |
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