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Role of Steric Effects on Rates of Hydrogen Atom Transfer Reactions

Cite this: J. Org. Chem. 2023, 88, 17, 12668–12676
Publication Date (Web):August 21, 2023
https://doi.org/10.1021/acs.joc.3c01361
Copyright © 2023 American Chemical Society

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    Abstract

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    The influence of steric effects on the rates of hydrogen atom transfer (HAT) reactions between oxyradicals and alkanes is explored computationally. Quantum chemical density functional theory computations of transition states show that activation barriers and reaction enthalpies are both influenced by bulky substituents on the radical but very little by substituents on the alkane. The activation barriers remain roughly correlated with reaction enthalpies via the Evans–Polanyi relationship even when steric repulsion effects become important, although dispersion effects sometimes stabilize transition states. By making comparisons to previously developed Evans–Polanyi and modified Roberts–Steel relationships, we find that HAT reactions between bulky molecules remain well-described by these relationships.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.3c01361.

    • Cartesian coordinates of all the structures as well as their computed thermodynamic enthalpies at room temperature, computed electronegativities of radicals used in the simplified Roberts–Steel plots, and all data needed to construct the Evans–Polanyi and Roberts–Steel plots (PDF)

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    Cited By

    This article is cited by 1 publications.

    1. Hao Liu, Ken D. Shimizu. Contributions of London Dispersion Forces to Solution-Phase Association Processes. Accounts of Chemical Research 2023, 56 (24) , 3572-3580. https://doi.org/10.1021/acs.accounts.3c00539

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