Murillo Jesse, Goodwin Conrad A P, Stevens Lauren, Fortier Skye, Gaunt Andrew J, Scott Brian L
Department of Chemistry and Biochemistry, University of Texas at El Paso El Paso Texas 79968 USA
Chemistry Division, Los Alamos National Laboratory Los Alamos New Mexico 87545 USA
Chem Sci. 2023 Jun 20;14(27):7438-7446. doi: 10.1039/d3sc02194g. eCollection 2023 Jul 12.
Reaction of the terphenyl bis(anilide) ligand [{K(DME)}L] (L = {CH[(2,6-PrCH)NCH]}) with trivalent chloride "MCl" salts (M = Ce, U, Np) yields two distinct products; neutral LM(Cl)(THF) (1) (M = Np, Ce), and the "-ate" complexes [K(DME)][(L)Np(Cl)] (2) or ([LM(Cl)(μ-K(X))]) (2, 2) (M = Ce, U) (X = DME or EtO) (2). Alternatively, analogous reactions with the iodide [MI(THF)] salts provide access to the neutral compounds LM(I)(THF) (3) (M = Ce, U, Np, Pu). All complexes exhibit close arene contacts suggestive of -interactions with the central arene ring of the terphenyl backbone, with 3 comprising the first structurally characterized Pu -arene moiety. Notably, the metal-arene bond metrics diverge from the predicted trends of metal-carbon interactions based on ionic radii, with the uranium complexes exhibiting the shortest M-C distance in all cases. Overall, the data presents a systematic study of f-element M--arene complexes across the early actinides U, Np, Pu, and comparison to cerium congeners.
三联苯双（苯胺）配体[{K（DME）}L]（L = {CH[(2,6-PrCH)NCH]})与三价氯化物“MCl”盐（M = Ce、U、Np）反应生成两种不同的产物；中性的LM(Cl)(THF)（1）（M = Np、Ce），以及“-ate”配合物[K(DME)][(L)Np(Cl)]（2）或（[LM(Cl)(μ-K(X))]）（2, 2）（M = Ce、U）（X = DME或EtO）（2）。或者，与碘化物[MI(THF)]盐进行类似反应可得到中性化合物LM(I)(THF)（3）（M = Ce、U、Np、Pu）。所有配合物都表现出紧密的芳烃接触，表明与三联苯主链的中心芳烃环存在π-相互作用，其中3包含首个结构表征的Pu-芳烃部分。值得注意的是，金属-芳烃键的度量偏离了基于离子半径预测的金属-碳相互作用趋势，在所有情况下铀配合物的M-C距离最短。总体而言，这些数据对早期锕系元素U、Np、Pu的f元素M-芳烃配合物进行了系统研究，并与铈同系物进行了比较。
