4.8 Article

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

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 31, 页码 11876-11879

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AMER CHEMICAL SOC
DOI: 10.1021/ja204008u

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  1. NRF of Korea through GRL [2010-00353]
  2. WCU [R31-2008-000-10010-0]
  3. KRICT OASIS
  4. NRF [2009-C1AAA001-2009-0093879]

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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.

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