Experiment and theory reveal the fundamental difference between two-state and single-state reactivity patterns in nonheme FeIV=O versus Ru IV=O oxidants

Sunder N. Dhuri; Sook Seo Mi; Yong Min Lee; Hajime Hirao; Yong Wang; Wonwoo Nam; Sason Shaik

doi:10.1002/anie.200705880

Experiment and theory reveal the fundamental difference between two-state and single-state reactivity patterns in nonheme Fe^IV=O versus Ru ^IV=O oxidants

Sunder N. Dhuri, Sook Seo Mi, Yong Min Lee, Hajime Hirao, Yong Wang, Wonwoo Nam, Sason Shaik

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

74 Scopus citations

Abstract

(Chemical Equation Presented) Two-state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of Fe^IV oxo complexes in O-transfer and H-abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with Ru^IV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible.

Original language	English
Pages (from-to)	3356-3359
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	47
Issue number	18
DOIs	https://doi.org/10.1002/anie.200705880
State	Published - 21 Apr 2008

Keywords

Bioinorganic chemistry
Iron
Oxo ligands
Reaction mechanisms
Ruthenium

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10.1002/anie.200705880

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title = "Experiment and theory reveal the fundamental difference between two-state and single-state reactivity patterns in nonheme FeIV=O versus Ru IV=O oxidants",

abstract = "(Chemical Equation Presented) Two-state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of FeIV oxo complexes in O-transfer and H-abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with RuIV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible.",

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AU - Dhuri, Sunder N.

AU - Mi, Sook Seo

AU - Lee, Yong Min

AU - Hirao, Hajime

AU - Wang, Yong

AU - Nam, Wonwoo

AU - Shaik, Sason

PY - 2008/4/21

Y1 - 2008/4/21

N2 - (Chemical Equation Presented) Two-state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of FeIV oxo complexes in O-transfer and H-abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with RuIV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible.

AB - (Chemical Equation Presented) Two-state reactivity involving close triplet ground and quintet excited states is responsible for the opposite reactivity trends of FeIV oxo complexes in O-transfer and H-abstraction reactions in dependence on the electron richness of the axial ligand X (see picture), as shown by comparison with RuIV analogues, in which both reactivities are solely governed by the electrophilicity of the complex because the quintet state is inaccessible.

KW - Bioinorganic chemistry

KW - Iron

KW - Oxo ligands

KW - Reaction mechanisms

KW - Ruthenium

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Experiment and theory reveal the fundamental difference between two-state and single-state reactivity patterns in nonheme Fe^IV=O versus Ru ^IV=O oxidants

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