Murillo Jesse, Bhowmick Rina, Harriman Katie L M, Gomez-Torres Alejandra, Wright Joshua, Miró Pere, Metta-Magaña Alejandro, Murugesu Muralee, Vlaisavljevich Bess, Fortier Skye
Department of Chemistry and Biochemistry, University of Texas at El Paso, El Paso, Texas 79968, USA.
Department of Chemistry, University of South Dakota, Vermillion, South Dakota 57069, USA.
Chem Commun (Camb). 2022 Aug 11;58(65):9112-9115. doi: 10.1039/d2cc03238d.
An unprecedented sandwich complex of the actinides is synthesized from the treatment of [UI(HMPA)]I (HMPA = OP(NMe)) (2) with 3 equiv. of K(CH) to give the neutral, bis(arenide) species U(η-CH)(η-CH)(HMPA) (1). Solid-state X-ray, SQUID magnetometry, and XANES analyses are consistent with tetravalent uranium supported by [CH] ligands. In one case, treatment of with an equiv. of AgOTf led to the isolation of U(η-CH)(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.
通过用3当量的K(CH)处理[UI(HMPA)]I（HMPA = OP(NMe)）（2）合成了一种前所未有的锕系元素夹心配合物，得到中性双（芳基）物种U(η-CH)(η-CH)(HMPA)（1）。固态X射线、超导量子干涉仪磁力测量和X射线吸收近边结构分析与由[CH]配体支撑的四价铀一致。在一种情况下，用等当量的AgOTf处理得到了由环迁移和配位迁移重排形成的U(η-CH)(HMPA)(THF)（3）。完全活性空间（CASSCF）计算表明U-C键仅由π相互作用组成，呈现出与经典锕系元素夹心化合物不同的独特电子结构。
