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On the Interpretation of Deuterium Kinetic Isotope Effects in C[BOND]H Bond Functionalizations by Transition-Metal Complexes


  • We thank the NSF (CHE-0910641 to J.F.H.) and NIH (GM087901 to E.M.S.) for funding of this work. We are grateful to Prof. Robert G. Bergman for providing a critical reading of an early draft of this essay, and to two referees for their valuable comments and suggestions.


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Rate versus selectivity determining: The measurement of a kinetic isotope effect (KIE) can provide valuable information about the mechanism of a reaction, but care must be taken in the design and interpretation of KIE experiments. Depending on the experiment that is conducted, the observation of a primary KIE resulting from H/D substitution does not necessarily imply that C[BOND]H bond cleavage occurs during the rate-determining step of a reaction. FG=functional group.

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