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Liberating the Anion: Evaluating Weakly Coordinating Cations

Cite this: J. Org. Chem. 2022, 87, 22, 15466–15482
Publication Date (Web):November 8, 2022
https://doi.org/10.1021/acs.joc.2c02001
Copyright © 2022 American Chemical Society

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    Abstract

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    A series of commonly used weakly coordinating cations (WCCs) including tetraalkylammonium, bis(triphenylphosphine)iminium (PPN), P2 and P5 phosphazenium, and tetraphenylphosphonium ions were investigated along with five additional tetraarylphosphonium ions [Ar = 4-Me, 4-t-Bu, 3,5-Me2, 4-Me2N, and 3,5-(MeO)2 phenyl derivatives]. Dissociation enthalpies of their chloride complexes were computed in the gas phase and in dichloromethane. These results are compared to infrared spectra of these salts in chloroform-d which provide free and bound C–D stretches, 19F NMR spectra of the corresponding tetrafluoroborate salts, ion-pair equilibrium constants, and reaction rates of the chlorides and acetates with 1-iodooctane. The latter transformation was also carried out under catalytic conditions. Substituted tetraphenylphosphonium ion derivatives are found to be surprisingly good WCCs that function as well or better than the P2 and P5 phosphazenium ions, the current WCC gold standard.

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.joc.2c02001.

    • Kinetic data, NMR and IR spectra, computed structures and energies, ion-pairing equilibrium constants, and the complete citation to ref (85) (PDF)

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    Cited By

    This article is cited by 2 publications.

    1. Stephen H. Dempsey, Wenjin Cao, Xue-Bin Wang, Steven R. Kass. Anion-Activated Bases and Nucleophiles Characterized by Photoelectron Spectroscopy. The Journal of Physical Chemistry A 2023, 127 (42) , 8828-8833. https://doi.org/10.1021/acs.jpca.3c04479
    2. Stephen H. Dempsey, Alex Lovstedt, Steven R. Kass. Electrostatically Enhanced 3- and 4-Pyridyl Borate Salt Nucleophiles and Bases. The Journal of Organic Chemistry 2023, 88 (15) , 10525-10538. https://doi.org/10.1021/acs.joc.3c00523

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