ACS Publications. Most Trusted. Most Cited. Most Read
Heavy Atom Secondary Kinetic Isotope Effect on H-Tunneling

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:J. Phys. Chem. A 2018, 122, 5, 1488-1495
    Article

    Heavy Atom Secondary Kinetic Isotope Effect on H-Tunneling
    Click to copy article linkArticle link copied!

    View Author Information
    Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17, 35392 Giessen, Germany
    *P. R. Schreiner. E-mail: [email protected]
    Other Access OptionsSupporting Information (1)

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2018, 122, 5, 1488–1495
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.7b12118
    Published January 10, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Abstract

    Click to copy section linkSection link copied!
    Abstract Image

    Although frequently employed, heavy atom kinetic isotope effects (KIE) have not been reported for quantum mechanical tunneling reactions. Here we examine the secondary KIE through 13C-substitution of the carbene atom in methylhydroxycarbene (H3C–C̈–OH) in its [1,2]H-tunneling shift reaction to acetaldehyde (H3C–CHO). Our study employs matrix-isolation IR spectroscopy in various inert gases and quantum chemical computations. Depending on the choice of the matrix host gas, the KIE varies within a range of 1.0 in xenon to 1.4 in neon. A KIE of 1.1 was computed using the Wentzel−Kramers−Brillouin (WKB) CVT/SCT, and instanton approaches for the gas phase at the B3LYP/cc-pVTZ level of theory. Computations with explicit consideration of the noble gas environment indicate that the surrounding atoms influence the tunneling reaction barrier height and width. The tunneling half-lives computed with the WKB approach are in good agreement with the experimental results in the different noble gases.

    Copyright © 2018 American Chemical Society

    Subjects

    what are subjects

    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 on the ACS Publications website at DOI: 10.1021/acs.jpca.7b12118.

    • Description of the experimental procedures, detailed matrix-isolation spectra, tables with assigned vibrational frequencies, a description of the employed kinetic analysis, a description of the employed theoretical methods and the geometries, electronic and zero-point vibrational energies and the complete citation for ref 27 and 36 (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
    powered by  Scite

    This article is cited by 20 publications.

    1. Andressa V. Müller, Shahbaz Ahmad, Jake T. Sirlin, Mehmed Z. Ertem, Dmitry E. Polyansky, David C. Grills, Gerald J. Meyer, Renato N. Sampaio, Javier J. Concepcion. Reduction of CO to Methanol with Recyclable Organic Hydrides. Journal of the American Chemical Society 2024, 146 (15) , 10524-10536. https://doi.org/10.1021/jacs.3c14605
    2. Mathias Paul, Thomas Thomulka, Wacharee Harnying, Jörg-Martin Neudörfl, Charlie R. Adams, Jonathan Martens, Giel Berden, Jos Oomens, Anthony J. H. M. Meijer, Albrecht Berkessel, Mathias Schäfer. Hydrogen Bonding Shuts Down Tunneling in Hydroxycarbenes: A Gas-Phase Study by Tandem-Mass Spectrometry, Infrared Ion Spectroscopy, and Theory. Journal of the American Chemical Society 2023, 145 (22) , 12124-12135. https://doi.org/10.1021/jacs.3c01698
    3. Tim Schleif, Melania Prado Merini, Stefan Henkel, Wolfram Sander. Solvation Effects on Quantum Tunneling Reactions. Accounts of Chemical Research 2022, 55 (16) , 2180-2190. https://doi.org/10.1021/acs.accounts.2c00151
    4. Edyta M. Greer, Victor Siev, Ayelet Segal, Alexander Greer, Charles Doubleday. Computational Evidence for Tunneling and a Hidden Intermediate in the Biosynthesis of Tetrahydrocannabinol. Journal of the American Chemical Society 2022, 144 (17) , 7646-7656. https://doi.org/10.1021/jacs.1c11981
    5. Eric R. Heller, Jeremy O. Richardson. Spin Crossover of Thiophosgene via Multidimensional Heavy-Atom Quantum Tunneling. Journal of the American Chemical Society 2021, 143 (49) , 20952-20961. https://doi.org/10.1021/jacs.1c10088
    6. Cláudio M. Nunes, André K. Eckhardt, Igor Reva, Rui Fausto, Peter R. Schreiner. Competitive Nitrogen versus Carbon Tunneling. Journal of the American Chemical Society 2019, 141 (36) , 14340-14348. https://doi.org/10.1021/jacs.9b06869
    7. Junjie Jiang, Longtian Huang, Bifeng Zhu, Wenbin Fan, Lina Wang, Igor Ying Zhang, Wei Fang, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng. Hydrogen‐Bonded Complexes of HPN⋅ and HNP⋅ Radicals with Carbon Monoxide. Angewandte Chemie International Edition 2025, 64 (2) https://doi.org/10.1002/anie.202414456
    8. Junjie Jiang, Longtian Huang, Bifeng Zhu, Wenbin Fan, Lina Wang, Igor Ying Zhang, Wei Fang, Tarek Trabelsi, Joseph S. Francisco, Xiaoqing Zeng. Hydrogen‐Bonded Complexes of HPN⋅ and HNP⋅ Radicals with Carbon Monoxide. Angewandte Chemie 2025, 137 (2) https://doi.org/10.1002/ange.202414456
    9. Haiting Lin, Anyi Chen, Tianren Liu, Wensheng Zhang, Xinyv Du, Junjie Feng, Jiajun Zeng, Yingying Fan, Dongxue Han, Li Niu. Synergistically Photocatalytic Conversion of Two Greenhouse Gases to Liquid‐Phase Oxygenates under Anaerobic Conditions. Solar RRL 2024, 8 (18) https://doi.org/10.1002/solr.202400522
    10. Benjamin W.J. Chen. Equilibrium and kinetic isotope effects in heterogeneous catalysis: A density functional theory perspective. Catalysis Communications 2023, 177 , 106654. https://doi.org/10.1016/j.catcom.2023.106654
    11. Omer Kirshenboim, Alexander Frenklah, Sebastian Kozuch. Switch chemistry at cryogenic conditions: quantum tunnelling under electric fields. Chemical Science 2021, 12 (9) , 3179-3187. https://doi.org/10.1039/D0SC06295B
    12. N. Fabian Kleimeier, André K. Eckhardt, Peter R. Schreiner, Ralf I. Kaiser. Interstellar Formation of Biorelevant Pyruvic Acid (CH3COCOOH). Chem 2020, 6 (12) , 3385-3395. https://doi.org/10.1016/j.chempr.2020.10.003
    13. Weiyu Qian, Xianxu Chu, Chao Song, Zhuang Wu, Mengqi Jiao, Hanwen Liu, Bin Zou, Guntram Rauhut, David P. Tew, Lina Wang, Xiaoqing Zeng. Hydrogen‐Atom Tunneling in Metaphosphorous Acid. Chemistry – A European Journal 2020, 26 (37) , 8205-8209. https://doi.org/10.1002/chem.202000844
    14. Itzhak Sedgi, Sebastian Kozuch. Heavy-atom tunnelling in Cu( ii )N 6 complexes: theoretical predictions and experimental manifestation. Chemical Science 2020, 11 (10) , 2828-2833. https://doi.org/10.1039/D0SC00160K
    15. Timothy A. H. Burd, Xiao Shan, David C. Clary. Hydrogen tunnelling in the rearrangements of carbenes: the role of dynamical calculations. Physical Chemistry Chemical Physics 2020, 22 (3) , 962-965. https://doi.org/10.1039/C9CP06300E
    16. Timothy A.H. Burd, Xiao Shan, David C. Clary. Tunnelling in cyclocarbenes: An application of Semiclassical Transition State Theory in reduced dimensions. Chemical Physics Letters 2019, 735 , 136783. https://doi.org/10.1016/j.cplett.2019.136783
    17. André K. Eckhardt, Frederik R. Erb, Peter R. Schreiner. Conformer-specific [1,2] H -tunnelling in captodatively-stabilized cyanohydroxycarbene (NC–C̈–OH). Chemical Science 2019, 10 (3) , 802-808. https://doi.org/10.1039/C8SC03720E
    18. Ashim Nandi, Adam Sucher, Sebastian Kozuch. Ping‐Pong Tunneling Reactions: Can Fluoride Jump at Absolute Zero?. Chemistry – A European Journal 2018, 24 (61) , 16348-16355. https://doi.org/10.1002/chem.201802782
    19. Curt Wentrup. Carbene und Nitrene: Aktuelle Entwicklungen in der Grundlagenchemie. Angewandte Chemie 2018, 130 (36) , 11680-11693. https://doi.org/10.1002/ange.201804863
    20. Curt Wentrup. Carbenes and Nitrenes: Recent Developments in Fundamental Chemistry. Angewandte Chemie International Edition 2018, 57 (36) , 11508-11521. https://doi.org/10.1002/anie.201804863
    Download PDF
    Go to The Journal of Physical Chemistry A
    Get e-Alerts
    Get e-Alerts

    The Journal of Physical Chemistry A

    Cite this: J. Phys. Chem. A 2018, 122, 5, 1488–1495
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpca.7b12118
    Published January 10, 2018
    Copyright © 2018 American Chemical Society
    Request reuse permissions

    Article Views

    1845

    Altmetric

    -

    Citations

    20
    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.