Interplay of Tunneling, Two-State Reactivity, and Bell-Evans-Polanyi Effects in C-H Activation by Nonheme Fe(IV)O Oxidants

Debasish Mandal; Sason Shaik

doi:10.1021/jacs.5b12077

Interplay of Tunneling, Two-State Reactivity, and Bell-Evans-Polanyi Effects in C-H Activation by Nonheme Fe(IV)O Oxidants

Debasish Mandal
, Sason Shaik^*

^*Corresponding author for this work

Institute of Chemistry

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

86 Scopus citations

Abstract

The study of C-H bond activation reactions by nonheme Fe^IVO species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIE_exp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.

Original language	English
Pages (from-to)	2094-2097
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	7
DOIs	https://doi.org/10.1021/jacs.5b12077
State	Published - 2 Mar 2016

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© 2016 American Chemical Society.

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abstract = "The study of C-H bond activation reactions by nonheme FeIVO species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIEexp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.",

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N2 - The study of C-H bond activation reactions by nonheme FeIVO species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIEexp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.

AB - The study of C-H bond activation reactions by nonheme FeIVO species with nine hydrocarbons shows that the kinetic isotope effect (KIE) involves strong tunneling and is a signature of the reactive spin states. Theory reproduces the observed spike-like appearance of plots of KIEexp against the C-H bond dissociation energy, and its origins are discussed. The experimentally observed Bell-Evans-Polanyi correlations, in the presence of strong tunneling, are reproduced, and the pattern is rationalized.

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Interplay of Tunneling, Two-State Reactivity, and Bell-Evans-Polanyi Effects in C-H Activation by Nonheme Fe(IV)O Oxidants

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