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Potential energy as a function of donor acceptor distance. For hydrogen transfer, this has been proposed to lead from transfer through the barrier (a) to an over-the-barrier process (b).112 As discussed in the text, while this scenario may, in certain instances, explain proton transfer between heteroatoms, it does not offer a theoretically-based explanation for the range of KIEs and their temperature dependencies observed in enzymatic C-H cleavage reactions.
