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 Jr.

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 Jr.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

113 Citations (Scopus)

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. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

Original language	English
Pages (from-to)	1291-1295
Journal	Angewandte Chemie - International Edition
Volume	48
Issue number	7
DOIs	https://doi.org/10.1002/anie.200804029
Publication status	Published - 2 Feb 2009
Externally published	Yes

Research 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. {\textcopyright} 2009 Wiley-VCH Verlag GmbH \& Co. KGaA.",

keywords = "Bioinorganic chemistry, Iron, Isotope effects, Isotopic labeling, Two-state reactivity",

author = "Klinker, \{Eric J.\} and Sason Shaik and Hajime Hirao and \{Que Jr.\}, Lawrence",

year = "2009",

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doi = "10.1002/anie.200804029",

language = "English",

volume = "48",

pages = "1291--1295",

journal = "Angewandte Chemie - International Edition",

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publisher = "John Wiley \& Sons",

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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. / Klinker, Eric J.; Shaik, Sason; Hirao, Hajime et al.
In: Angewandte Chemie - International Edition, Vol. 48, No. 7, 02.02.2009, p. 1291-1295.

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

TY - JOUR

T1 - A two-state reactivity model explains unusual kinetic isotope effect patterns in C-H bond cleavage by nonheme oxoiron(IV) complexes

AU - Klinker, Eric J.

AU - Shaik, Sason

AU - Hirao, Hajime

AU - Que Jr., Lawrence

PY - 2009/2/2

Y1 - 2009/2/2

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. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

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. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

KW - Bioinorganic chemistry

KW - Iron

KW - Isotope effects

KW - Isotopic labeling

KW - Two-state reactivity

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U2 - 10.1002/anie.200804029

DO - 10.1002/anie.200804029

M3 - RGC 21 - Publication in refereed journal

C2 - 19130517

SN - 1433-7851

VL - 48

SP - 1291

EP - 1295

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 7

ER -

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

Abstract

Research Keywords

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