ACS Publications. Most Trusted. Most Cited. Most Read
Role of Steric Effects on Rates of Hydrogen Atom Transfer Reactions
My Activity

Figure 1Loading Img
    Article

    Role of Steric Effects on Rates of Hydrogen Atom Transfer Reactions
    Click to copy article linkArticle link copied!

    Other Access OptionsSupporting Information (1)

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2023, 88, 17, 12668–12676
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.3c01361
    Published August 21, 2023
    Copyright © 2023 American Chemical Society

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    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.

    Copyright © 2023 American Chemical Society

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.

    Recommended

    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. Add or change your institution or let them know you’d like them to include access.

    Supporting Information

    Click to copy section linkSection link copied!

    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)

    Terms & Conditions

    Electronic Supporting Information files are available without a subscription to ACS Web Editions. The American Chemical Society holds a copyright ownership interest in any copyrightable Supporting Information. Files available from the ACS website may be downloaded for personal use only. Users are not otherwise permitted to reproduce, republish, redistribute, or sell any Supporting Information from the ACS website, either in whole or in part, in either machine-readable form or any other form without permission from the American Chemical Society. For permission to reproduce, republish and redistribute this material, requesters must process their own requests via the RightsLink permission system. Information about how to use the RightsLink permission system can be found at http://pubs.acs.org/page/copyright/permissions.html.

    Cited By

    Click to copy section linkSection link copied!
    Citation Statements
    Explore this article's citation statements on scite.ai

    This article is cited by 6 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
    2. Yi Sun. Efficient acceleration of the convergence of the minimum free energy path via a path‐planning generated initial guess. Journal of Computational Chemistry 2025, 46 (1) https://doi.org/10.1002/jcc.27504
    3. Shuaipeng Wang, Hongwei Li, Linqing Guo, Sen Zhang, Yunfei Xu, YinBo Zhu, Xiaoyi Liu, Jinchun Shi. Kinetic study of hydrogen abstraction and unimolecular decomposition reactions of diethylamine during pyrolysis and oxidation. International Journal of Hydrogen Energy 2024, 94 , 1-12. https://doi.org/10.1016/j.ijhydene.2024.10.425
    4. Javier E. Alfonso-Ramos, Rebecca M. Neeser, Thijs Stuyver. Repurposing quantum chemical descriptor datasets for on-the-fly generation of informative reaction representations: application to hydrogen atom transfer reactions. Digital Discovery 2024, 3 (5) , 919-931. https://doi.org/10.1039/D4DD00043A
    5. Xiahe Chen, Yun-Fang Yang, Yuanbin She. Synchronous and basic asynchronous hydrogen-atom abstraction of benzylic substrates by high-valent iron–oxo porphyrin species. Organic Chemistry Frontiers 2024, 11 (4) , 1039-1049. https://doi.org/10.1039/D3QO01827J
    6. Tonggang Hao, Jiahao Shen, Yin Wei, Min Shi. Alkene difunctionalization enabled by photocatalytic hydrogen atom transfer from haloalkane α-C(sp3)–H bonds. Chem Catalysis 2023, 3 (12) , 100807. https://doi.org/10.1016/j.checat.2023.100807

    The Journal of Organic Chemistry

    Cite this: J. Org. Chem. 2023, 88, 17, 12668–12676
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.joc.3c01361
    Published August 21, 2023
    Copyright © 2023 American Chemical Society

    Article Views

    1440

    Altmetric

    -

    Citations

    Learn about these metrics

    Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

    Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

    The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.