Organometallic Chemistry

Actinide Arene-Metalates: 2. A Neutral Uranium Bis(Anthracenide) Sandwich Complex and Elucidation of its Electronic Structure



An unprecedented sandwich complex of the actinides is synthesized from the treatment of [UI2(HMPA)4]I (HMPA = OP(NMe2)3) (2) with 3 equiv. of K[C14H10] to give the neutral, bis(arenide) species U(η6-C14H10)(η4-C14H10)(HMPA)2 (1). Solid-state X-ray, SQUID magnetometry, and XANES analyses are consistent with tetravalent uranium supported by [C14H10]2- ligands. In one case, treatment of 1 with an equiv. of AgOTf led to the isolation of U(η6-C14H10)2(HMPA)(THF) (3), formed from ring migration and haptotropic rearrangement. Complete active space (CASSCF) calculations indicate the U-C bonding to solely consist of π-interactions, presenting a unique electronic structure distinct from classic actinide sandwich compounds.


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Supplementary material

Thumbnail image of Supp Info - U anth HMPA - 2022_05_19.pdf
Supporting Information File for Actinide Arene-Metalates 2.
Supporting Information File for Actinide Arene-Metalates 2.