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

Jesse Murillo; Rina Bhowmick; Katie L M Harriman; Alejandra Gomez-Torres; Joshua Wright; Pere Miró; Alejandro Metta-Magaña; Muralee Murugesu; Bess Vlaisavljevich; Skye Fortier

doi:10.1039/d2cc03238d

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

Chem Commun (Camb). 2022 Aug 11;58(65):9112-9115. doi: 10.1039/d2cc03238d.

Affiliations

¹ Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA. asfortier@utep.edu.
² Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, USA. Bess.Vlaisavljevich@usd.edu.
³ Department of Chemistry and Biomolecular Sciences, University of Ottawa, Ottawa, Ontario K1N 6N5, Canada.
⁴ Department of Physics, Illinois Institute of Technology, Chicago, IL, 60616, USA.

PMID: 35880486
DOI: 10.1039/d2cc03238d

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.