硝基亚苯的氧化还原非惰性镍。
Redox Non-Innocence of Nitrosobenzene at Nickel.
机构信息
Department of Chemistry, Georgetown University, Box 571227, Washington, DC, 20057-1227, USA.
Inorganic, Isotope and Actinide Chemistry, Los, Alamos National Laboratory, Los Alamos, NM, 87545, USA.
出版信息
Angew Chem Int Ed Engl. 2016 Aug 22;55(35):10321-5. doi: 10.1002/anie.201605026. Epub 2016 Jul 29.
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.
亚硝基苯（PhNO）可用作亚硝酰自由基（HNO）的稳定类似物，后者是一种具有生物学相关性的氧化还原活性的一氧化氮衍生物。电子缺的β-二酮亚胺镍（I）配合物[(i) Pr2 NNF6 ]Ni 捕获亚硝基苯，导致 PhNO 配体还原为（PhNO）（./-）物种，与 [(i) Pr2 NNF6 ]Ni(η(2) -ONPh)中的平面四方 Ni(II)中心配位。配体中心的还原导致（PhNO）（2-）部分与 Ni(II)结合，XAS 研究支持这一结果。对（PhNO）（./-）和（PhNO）（2-）配体的结构-反应性模式的系统研究揭示了与超氧（O2 ）（./-）和过氧（O2 ）（2-）配体的相似性，分别预测了更短暂的 HNO 配体的反应性模式。
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