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

Author(s)
Hong, SeungwooLee, Yong-MinCho, Kyung-BinSundaravel, KaruppasamyCho, JaeheungKirn, Myoung JinShin, WoonsupNam, Wonwoo
Issued Date
2011-08
DOI
10.1021/ja204008u
URI
https://scholarworks.unist.ac.kr/handle/201301/48140
Fulltext
https://pubs.acs.org/doi/10.1021/ja204008u
Citation
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.133, no.31, pp.11876 - 11879
Abstract
Mononuclear nonheme iron(IV)-oxo complexes with two different topologies, cis-α-[FeIV(O)(BQCN)]2+ and cis-β-[FeIV(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-α-[FeIV(O)(BQCN)]2+ was more reactive than cis-β-[FeIV(O)(BQCN)]2+ in the oxidation reactions. The reactivity difference between the cis-α and cis-β isomers of [FeIV(O)(BQCN)]2+ was rationalized with the FeIV/III redox potentials of the iron(IV)-oxo complexes: the FeIV/III redox potential of the cis-α isomer was 0.11 V higher than that of the cis-β isomer.
Publisher
AMER CHEMICAL SOC
ISSN
0002-7863
Keyword
ELECTRON-TRANSFER PROPERTIESSPIN OXOIRON(IV) COMPLEXSPECTROSCOPIC CHARACTERIZATIONOXIDATION CATALYSISCORRELATION-ENERGYCRYSTAL-STRUCTUREDENSITYEXCHANGEOXOIRON(II)

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