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Facile Oxidation of Ce(III) to Ce(IV) Using Cu(I) Salts
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    Facile Oxidation of Ce(III) to Ce(IV) Using Cu(I) Salts
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2024, 63, 21, 9602–9609
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    https://doi.org/10.1021/acs.inorgchem.3c04337
    Published March 20, 2024
    Copyright © 2024 American Chemical Society

    Abstract

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    The synthesis, luminescence, and electrochemical properties of the Ce(III) compound, [(C5Me5)2(2,6-iPr2C6H3O)Ce(THF)], 1, were investigated. Based on the electrochemical data, treatment of 1 with CuX (X = Cl, Br, I) results in the formation of the corresponding Ce(IV) complexes, [(C5Me5)2(2,6-iPr2C6H3O)Ce(X)]. Each complex has been characterized using NMR, IR, and UV–vis spectroscopy as well as structurally determined using X-ray crystallography. Additionally, the treatment of [(C5Me5)2(2,6-iPr2C6H3O)Ce(Br)] with AgF results in the formation of the putative [(C5Me5)2(2,6-iPr2C6H3O)Ce(F)]. The electronic structure of these Ce(IV)–X complexes was investigated by bond analyses and the Ce(IV)–F moiety using quantum chemistry NMR calculations.

    Copyright © 2024 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.inorgchem.3c04337.

    • Experimental, crystallographic, electrochemical, and computational details, including NMR, IR, UV–vis, and luminescence spectra (PDF)

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    CCDC 23116272311629 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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    Cited By

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    This article is cited by 2 publications.

    1. Conrad A. P. Goodwin, (Guest Editor)Jordan F. Corbey (Guest Editor). Ligand–Metal Complementarity in Rare-Earth and Actinide Chemistry. Inorganic Chemistry 2024, 63 (21) , 9355-9362. https://doi.org/10.1021/acs.inorgchem.4c01504
    2. Haruko Tateyama, Andrew C. Boggiano, Can Liao, Kaitlyn S. Otte, Xiaosong Li, Henry S. La Pierre. Tetravalent Cerium Alkyl and Benzyl Complexes. Journal of the American Chemical Society 2024, 146 (15) , 10268-10273. https://doi.org/10.1021/jacs.4c01964

    Inorganic Chemistry

    Cite this: Inorg. Chem. 2024, 63, 21, 9602–9609
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.inorgchem.3c04337
    Published March 20, 2024
    Copyright © 2024 American Chemical Society

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