Two-State Reactivity Model Explains Unusual Kinetic Isotope Effect Patterns in C----H Bond Cleavage by Nonheme Oxoiron(IV) Complexes

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...

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Published inAngewandte Chemie (International ed.) Vol. 48; no. 7; pp. 1291 - 1295
Main Authors Klinker, Eric J, Shaik, Sason, Hirao, Hajime, Que, Lawrence Jr
Format Journal Article
LanguageEnglish
Published Weinheim Wiley-VCH Verlag 01.01.2009
WILEY-VCH Verlag
WILEY‐VCH Verlag
Subjects
bioinorganic chemistry
Catalysis
Hydrocarbons - chemistry
Hydrocarbons - metabolism
iron
Iron - chemistry
Iron - metabolism
isotope effects
Isotope Labeling
Isotopes - chemistry
Isotopes - metabolism
isotopic labeling
Kinetics
Models, Chemical
Molecular Structure
Oxidation-Reduction
Oxygen - chemistry
Oxygen - metabolism
two-state reactivity
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Summary: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.
Bibliography:http://dx.doi.org/10.1002/anie.200804029
Ministry of Education and Research
ark:/67375/WNG-5L9LC8LJ-K
National Institutes of Health - No. GM-33162
JSPS Postdoctoral Fellowship for Research Abroad
ArticleID:ANIE200804029
We thank the National Institutes of Health (GM-33162 to L.Q.), the University of Minnesota Graduate School (dissertation fellowship to E.J.K.), the Ministry of Education and Research within the Framework of the German-Israeli Project Cooperation (DIP; to S.S.), and the JSPS Postdoctoral Fellowship for Research Abroad (to H.H.) for support of this research.
University of Minnesota Graduate School
German-Israeli Project Cooperation
istex:9E4ACA4FEA23E35B66B5A57CC864A93657ED3A2F
We thank the National Institutes of Health (GM‐33162 to L.Q.), the University of Minnesota Graduate School (dissertation fellowship to E.J.K.), the Ministry of Education and Research within the Framework of the German–Israeli Project Cooperation (DIP; to S.S.), and the JSPS Postdoctoral Fellowship for Research Abroad (to H.H.) for support of this research.
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ISSN:1433-7851
1521-3773
DOI:10.1002/anie.200804029