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[2π+2π] Cycloaddition of Isocyanates to Uranium(IV) Imido Complexes for the Synthesis of U(IV) κ2-Ureato Compounds

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H.C. Brown Laboratory, Department of Chemistry, Purdue University, West Lafayette, Indiana 47906, United States
Cite this: Inorg. Chem. 2017, 56, 4, 1956–1965
Publication Date (Web):February 6, 2017
Copyright © 2017 American Chemical Society

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    Abstract Image

    A new family of uranium(IV) imido complexes of the form Tp*2U(NR) (Tp* = hydrotris(3,5-dimethylpyrazolyl)borate; R = benzyl (Bn), para-tolyl (p-Tol), 2,6-diethylphenyl (detp), and 2,6-diisopropylphenyl (dipp)) have been generated by bibenzyl extrusion from Tp*2UBn. Tp*2U(NBn), Tp*2U(Np-Tol), and Tp*2U(Ndetp), along with previously reported Tp*2U(NPh) and Tp*2U(NAd) (Ad = 1-adamantyl), readily undergo [2π+2π] cycloaddition with isocyanates and isothiocyanates to generate κ2-ureato and κ2-thioureato derivatives, respectively. These new uranium(IV) complexes were characterized via multinuclear NMR, vibrational and electronic absorption spectroscopies, and, where possible, X-ray crystallography. The steric demands of the ligands were quantitatively assessed using computational modeling, and it was shown that cycloaddition only occurs for imido species where ligands occupy 90% or less of the coordination sphere.

    Supporting Information

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.inorgchem.6b02547.

    • CIF data of 2-Bn (CIF)

    • CIF data of 2-dipp (CIF)

    • CIF data of 2-pTol (CIF)

    • CIF data of 2-detp (CIF)

    • CIF data of 3-Ph (CIF)

    • CIF data of 4-Ph (CIF)

    • CIF data of 5-Ph (CIF)

    • 1H NMR spectra, 11B NMR spectra, IR spectra, electronic absorption spectroscopy, and crystallographic details (PDF)

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