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Actinide arene-metalates: 2. A neutral uranium bis(anthracenide) sandwich complex and elucidation of its electronic structure.

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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… Click to show full abstract

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.

Keywords: sandwich; bis; electronic structure; sandwich complex; hmpa

Journal Title: Chemical communications
Year Published: 2022

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