A two-state reactivity model explains unusual kinetic isotope effect patterns in C-H bond cleavage by nonheme oxoiron(IV) complexes

Eric J. Klinker; Sason Shaik; Hajime Hirao; Lawrence Que

doi:10.1002/anie.200804029

A two-state reactivity model explains unusual kinetic isotope effect patterns in C-H bond cleavage by nonheme oxoiron(IV) complexes

Eric J. Klinker
, Sason Shaik
, Hajime Hirao
, Lawrence Que

Institute of Chemistry

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

112 Scopus citations

Abstract

It's in the bond: The cleavage of C H bonds by two related oxoiron(IV) complexes shows a range of kinetic isotope effect (KIE) values that exhibit an unusual dependence on the C H bond strength. Large nonclassical KIEs are observed for bond strengths below 93 kcal mol^-1, while semiclassical values are found above this value (see graph, DHA=9,10- dihydroanthracene). This nonintuitive behavior can be rationalized by invoking a two-state reactivity model.

Original language	English
Pages (from-to)	1291-1295
Number of pages	5
Journal	Angewandte Chemie - International Edition
Volume	48
Issue number	7
DOIs	https://doi.org/10.1002/anie.200804029
State	Published - 2 Feb 2009

Keywords

Bioinorganic chemistry
Iron
Isotope effects
Isotopic labeling
Two-state reactivity

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10.1002/anie.200804029

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title = "A two-state reactivity model explains unusual kinetic isotope effect patterns in C-H bond cleavage by nonheme oxoiron(IV) complexes",

abstract = "It's in the bond: The cleavage of C H bonds by two related oxoiron(IV) complexes shows a range of kinetic isotope effect (KIE) values that exhibit an unusual dependence on the C H bond strength. Large nonclassical KIEs are observed for bond strengths below 93 kcal mol-1, while semiclassical values are found above this value (see graph, DHA=9,10- dihydroanthracene). This nonintuitive behavior can be rationalized by invoking a two-state reactivity model.",

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AU - Hirao, Hajime

AU - Que, Lawrence

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N2 - It's in the bond: The cleavage of C H bonds by two related oxoiron(IV) complexes shows a range of kinetic isotope effect (KIE) values that exhibit an unusual dependence on the C H bond strength. Large nonclassical KIEs are observed for bond strengths below 93 kcal mol-1, while semiclassical values are found above this value (see graph, DHA=9,10- dihydroanthracene). This nonintuitive behavior can be rationalized by invoking a two-state reactivity model.

AB - It's in the bond: The cleavage of C H bonds by two related oxoiron(IV) complexes shows a range of kinetic isotope effect (KIE) values that exhibit an unusual dependence on the C H bond strength. Large nonclassical KIEs are observed for bond strengths below 93 kcal mol-1, while semiclassical values are found above this value (see graph, DHA=9,10- dihydroanthracene). This nonintuitive behavior can be rationalized by invoking a two-state reactivity model.

KW - Bioinorganic chemistry

KW - Iron

KW - Isotope effects

KW - Isotopic labeling

KW - Two-state reactivity

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A two-state reactivity model explains unusual kinetic isotope effect patterns in C-H bond cleavage by nonheme oxoiron(IV) complexes

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