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Hydroxide Chemoselectivity Changes with Water Microsolvation
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    Physical Insights into Chemistry, Catalysis, and Interfaces

    Hydroxide Chemoselectivity Changes with Water Microsolvation
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    • Sapir Willdorf-Cohen
      Sapir Willdorf-Cohen
      The Wolfson Department of Chemical Engineering, Technion-Israel Institute of Technology, Haifa 3200003, Israel
    • Alexander Kaushansky
      Alexander Kaushansky
      Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 3200003, Israel
    • Dario R. Dekel*
      Dario R. Dekel
      The Wolfson Department of Chemical Engineering, Technion-Israel Institute of Technology, Haifa 3200003, Israel
      The Nancy & Stephen Grand Technion Energy Program (GTEP), Technion-Israel Institute of Technology, Haifa 3200003, Israel
      *Email: [email protected]
    • Charles E. Diesendruck*
      Charles E. Diesendruck
      Schulich Faculty of Chemistry, Technion-Israel Institute of Technology, Haifa 3200003, Israel
      The Nancy & Stephen Grand Technion Energy Program (GTEP), Technion-Israel Institute of Technology, Haifa 3200003, Israel
      *Email: [email protected]
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2022, 13, 43, 10216–10221
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    https://doi.org/10.1021/acs.jpclett.2c02637
    Published October 26, 2022
    Copyright © 2022 American Chemical Society

    Abstract

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    Solvent molecules are known to affect chemical reactions, especially if they interact with one or more of the reactants or catalysts. In ion microsolvation, i.e., solvent molecules in the first solvation sphere, strong electronic interactions are created, leading to significant changes in charge distribution and consequently on their nucleophilicity/electrophilicity and acidity/basicity. Despite a long history of research in the field, fundamental issues regarding the effects of ion microsolvation are still open, especially in the condensed phase. Using reactions between hydroxide and relatively stable quaternary ammonium salts as an example, we show that water microsolvation can change hydroxide’s chemoselectivity by differently affecting its basicity and nucleophilicity. In this example, the hydroxide reactivity as a nucleophile is less affected by water microsolvation than its reactivity as a base. These disparities are discussed by calculating and comparing oxidation potentials and polarizabilities of the different water–hydroxide clusters.

    Copyright © 2022 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpclett.2c02637.

    • Calculation of QA’s decomposition, NMR spectra, data from kinetics experiments, rate constant calculations, and computational results (PDF)

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    This article is cited by 11 publications.

    1. Ritu Kumari, Vineeta Chaturvedi, Mudit Pithi, Avik K. Pati. Microsolvation-Driven Hours-Long Spectral Dynamics in Phenoxazine Dyes. The Journal of Physical Chemistry A 2025, 129 (1) , 82-93. https://doi.org/10.1021/acs.jpca.4c06314
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    The Journal of Physical Chemistry Letters

    Cite this: J. Phys. Chem. Lett. 2022, 13, 43, 10216–10221
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jpclett.2c02637
    Published October 26, 2022
    Copyright © 2022 American Chemical Society

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