Ligand Topology Effect on the Reactivity of a Mononuclear Nonheme Iron(IV)-Oxo Complex in Oxygenation Reactions

  • Hong, Seungwoo
  • Lee, Yong-Min
  • Cho, Kyung-Bin
  • Sundaravel, Karuppasamy
  • Cho, Jaeheung
  • ... Shin, Woonsup
  • 외 2명
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초록

Mononuclear nonheme iron(IV)-oxo complexes with two different topologies, cis-alpha-[Fe(IV)(O)(BQCN)](2+) and cis-beta-[Fe(IV)(O)(BQCN)](2+), were synthesized and characterized with various spectroscopic methods. The effect of ligand topology on the reactivities of nonheme iron(IV)oxo complexes was investigated in C-H bond activation and oxygen atom-transfer reactions; cis-alpha-[Fe(IV)(O)(BQCN)](2+) was more reactive than cis-beta-[Fe(IV)(O)(BQCN)](2+) in the oxidation reactions. The reactivity difference between the cis-alpha and cis-beta isomers of [Fe(IV)(O)(BQCN)](2+) was rationalized with the Fe(IV/III) redox potentials of the iron(IV)-oxo complexes: the Fe(IV/III) redox potential of the cis-alpha isomer was 0.11 V higher than that of the cis-beta isomer.

키워드

ELECTRON-TRANSFER PROPERTIESSPIN OXOIRON(IV) COMPLEXSPECTROSCOPIC CHARACTERIZATIONOXIDATION CATALYSISCORRELATION-ENERGYCRYSTAL-STRUCTUREDENSITYEXCHANGEOXOIRON(II)
제목
Ligand Topology Effect on the Reactivity of a Mononuclear Nonheme Iron(IV)-Oxo Complex in Oxygenation Reactions
저자
Hong, SeungwooLee, Yong-MinCho, Kyung-BinSundaravel, KaruppasamyCho, JaeheungKirn, Myoung JinShin, WoonsupNam, Wonwoo
DOI
10.1021/ja204008u
발행일
2011-08-10
유형
Article
저널명
Journal of the American Chemical Society
133
31
페이지
11876 ~ 11879