Selective Formation of an Fe<sup>IV</sup>O or an Fe<sup>III</sup>OOH Intermediate From Iron(II) and H<sub>2</sub>O<sub>2</sub>: Controlled Heterolytic versus Homolytic Oxygen–Oxygen Bond Cleavage by the Second Coordination Sphere
作者: Dr. Khaled CheaibM. Qadri E. MubarakDr. Katell Sénéchal‐DavidDr. Christian HerreroDr. Régis GuillotDr. Martin ClémanceyDr. Jean‐Marc LatourDr. Sam P. de VisserProf. Jean‐Pierre MahyProf. Frédéric BanseDr. Frédéric Avenier
作者单位: 1Institut de Chimie Moléculaire et des matériaux d'Orsay (UMR 8182) Univ Paris Sud Université Paris Saclay 91405 Orsay cedex France
2 Manchester Institute of Biotechnology and School of Chemical Engineering and Analytical Science The University of Manchester 131 Princess Street Manchester M1 7DN UK
3 LCBM/PMB and CEA/BIG/CBM/ and CNRS UMR 5249 Université Grenoble Alpes Grenoble 38054 France
刊名: Angewandte Chemie International Edition, 2019, Vol.58 (3), pp.854-858
来源数据库: Wiley Journal
DOI: 10.1002/anie.201812724
关键词: Iron complexesN ligandsO−O bond breakingProton coupled electron transfer (PCET)
原始语种摘要: Abstract(#br)We demonstrate that the devised incorporation of an alkylamine group into the second coordination sphere of an FeII complex allows to switch its reactivity with H2O2 from the usual formation of FeIII species towards the selective generation of an FeIV‐oxo intermediate. The FeIV‐oxo species was characterized by UV/Vis absorption and Mössbauer spectroscopy. Variable‐temperature kinetic analyses point towards a mechanism in which the heterolytic cleavage of the O−O bond is triggered by a proton transfer from the proximal to the distal oxygen atom in the FeII‐H2O2 complex with the assistance of the pendant amine. DFT studies reveal that this heterolytic cleavage is actually...
全文获取路径: Wiley  (合作)
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关键词翻译
关键词翻译
  • II Interactive Interface
  • triggered 触发的
  • cleavage 解理
  • immediately 立即
  • heterolytic 异种溶解的
  • formation 建造
  • complex 超群
  • coupled 耦合
  • alkylamine 烷基胺
  • incorporation 掺合