A Two‐State Reactivity Model Explains Unusual Kinetic Isotope Effect Patterns in CH Bond Cleavage by Nonheme Oxoiron(IV) Complexes | Zendy

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

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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

Author(s) -

Klinker Eric J.,

Shaik Sason,

Hirao Hajime,

Que Lawrence

Publication year - 2009

Publication title -

angewandte chemie international edition

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 5.831

H-Index - 550

eISSN - 1521-3773

pISSN - 1433-7851

DOI - 10.1002/anie.200804029

Subject(s) - cleavage (geology) , reactivity (psychology) , kinetic isotope effect , kinetic energy , chemistry , bond cleavage , stereochemistry , isotope , computational chemistry , physics , organic chemistry , materials science , catalysis , deuterium , nuclear physics , quantum mechanics , medicine , alternative medicine , pathology , fracture (geology) , composite material

It's in the bond : The cleavage of CH bonds by two related oxoiron(IV) complexes shows a range of kinetic isotope effect (KIE) values that exhibit an unusual dependence on the CH 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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