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

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posted on 10.08.2011, 00:00 authored by Seungwoo Hong, Yong-Min Lee, Kyung-Bin Cho, Karuppasamy Sundaravel, Jaeheung Cho, Myoung Jin Kim, Woonsup Shin, Wonwoo Nam
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.