cPCET versus HAT: A Direct Theoretical Method for Distinguishing X-H Bond-Activation Mechanisms

Angewandte Chemie
Johannes E M N Klein, Gerald Knizia

Abstract

Proton-coupled electron transfer (PCET) events play a key role in countless chemical transformations, but they come in many physical variants which are hard to distinguish experimentally. While present theoretical approaches to treat these events are mostly based on physical rate coefficient models of various complexity, it is now argued that it is both feasible and fruitful to directly analyze the electronic N-electron wavefunctions of these processes along their intrinsic reaction coordinate (IRC). In particular, for model systems of lipoxygenase and the high-valent oxoiron(IV) intermediate TauD-J it is shown that by invoking the intrinsic bond orbital (IBO) representation of the wavefunction, the common boundary cases of hydrogen atom transfer (HAT) and concerted PCET (cPCET) can be directly and unambiguously distinguished in a straightforward manner.

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Citations

May 1, 2019·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Diego SorbelliJohannes E M N Klein
Jun 18, 2019·Angewandte Chemie·Jelte S SteenJohannes E M N Klein
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Sep 11, 2020·Chemical Communications : Chem Comm·Lorenzo D'AmoreMarcel Swart
May 31, 2019·Chemical Communications : Chem Comm·Youngsuk KimEunsung Lee
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Apr 29, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Yasuyuki YamadaKentaro Tanaka
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May 7, 2020·The Journal of Physical Chemistry Letters·Thomas A Corry, Patrick J O'Malley
Nov 4, 2020·Journal of Chemical Information and Modeling·Felipe Curtolo, Guilherme M Arantes
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Feb 12, 2019·Journal of the American Chemical Society·McKenna K Goetz, John S Anderson
Dec 3, 2021·Journal of the American Chemical Society·McKenna K GoetzJohn S Anderson

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