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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- 作者：Debasish Mandal ; Sason Shaik
- 刊名：Journal of the American Chemical Society
- 出版年：2016
- 出版时间：February 24, 2016
- 年：2016
- 卷：138
- 期：7
- 页码：2094-2097
- 全文大小：318K
- ISSN：1520-5126
文摘
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.