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

Chemistry (Twin Cities)

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

103 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 (US)
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 - Feb 2 2009

Keywords

Bioinorganic chemistry
Iron
Isotope effects
Isotopic labeling
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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