Homoleptic 1,2-benzenedithiolate complexes of thorium and uranium

Godinho, Gabriella S.; Ordoñez, Osvaldo; Feng, Qien; Wu, Guang; Hayton, Trevor W.

doi:10.1016/j.ica.2025.122943

Title: Homoleptic 1,2-benzenedithiolate complexes of thorium and uranium

Journal Article · Sun Oct 05 00:00:00 UTC 2025 · Inorganica Chimica Acta

DOI: https://doi.org/10.1016/j.ica.2025.122943 · OSTI ID:3014811

Godinho, Gabriella S. ^[1]; Ordoñez, Osvaldo ^[1]; Feng, Qien ^[1]; Wu, Guang ^[1]; Hayton, Trevor W. ^[1]

University of California, Santa Barbara, CA (United States)

Reaction of 4 equiv. of [Li(TMEDA)]₂[1,2-S₂C₆H₄] with [ThCl₄(DME)₂] or [UCl₄(THF)₃] in THF results in formation of [Li(THF)₂]₄[An(1,2-S₂C₆H₄)₄] (An = Th, 1; An = U, 2), whereas reaction of 4 equiv. of [Li(TMEDA)]₂[1,2-S₂C₆H₄] with UCl₄ in Et₂O results in formation of [Li(TMEDA)]₄[U(1,2-S₂C₆H₄)₄] (3). Complexes 1–3 represent the first reported benzenedithiolate complexes of the actinides. Here, they were characterized by NMR spectroscopy and X-ray crystallography. In the solid state, complexes 1–3 exhibit triangular dodecahedral geometries about their actinide centers. Additionally, their Li⁺ cations are bound by two sulfur atoms of adjacent [1,2-S₂C₆H₄]²⁻ ligands, in addition to two solvent donor atoms. In solution, complexes 2 and 3 exhibit spectral data consistent with S₄ symmetry (and non-exchanging Li⁺ sites), whereas complex 1 exhibits spectral properties consistent with labile Li⁺ cations.

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Research Organization:: University of California, Santa Barbara, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: SC0001861

OSTI ID:: 3014811

Journal Information:: Inorganica Chimica Acta, Journal Name: Inorganica Chimica Acta Vol. 589; ISSN 0020-1693

Publisher:: Elsevier BVCopyright Statement

Country of Publication:: United States

Language:: English

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