Concert along the Edge: Dynamics and the Nature of the Border between General and Specific Acid-Base Catalysis
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© 2017 American Chemical Society. Reactions that involve a combination of proton transfer and heavy-atom bonding changes are normally categorized by whether the proton transfer is occurring during the rate-limiting step, as in the distinction between general and specific acid-base catalysis. The experimental and computational study here of a β-ketoacid decarboxylation shows how the distinction between the two mechanisms breaks down near its border due to the differing time scales for proton versus heavy-atom motion. Isotope effects in the decarboxylation of benzoylacetic acid support a transition state in which the proton transfer is complete. In quasiclassical trajectories passing through this transition state, the new O-H bond after proton transfer undergoes several vibrations before heavy-atom motion completes the reaction. The bonding changes are thus temporally separated at a "dynamic intermediate" structure that acts equivalently to an ordinary intermediate in the trajectories, including the reversal of trajectories at the intermediate when the second "step" fails, but the structure is not an energy minimum. The results define a border between mechanisms where the usual energetic definition of intermediates is not meaningful.
author list (cited authors)
Aziz, H. R., & Singleton, D. A.
complete list of authors
Aziz, Hannah R||Singleton, Daniel A