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Abstract The study of actinide electronic structure and bonding within rigorously controlled environments is fundamental to advancing nuclear applications. Here, we report a new set of isostructural actinide organometallics; An(COT^big)₂, (An = Th, U, Np, and Pu), where COT^bigis the bulky 1,4-bis(triphenylsilyl)-substituted cyclooctatetraenyl dianion (1,4-(Ph₃Si)₂C₈H₆)^2-. The actinide(IV) metallocene sandwiches have a clam-shell structure, offering a new molecular symmetry to exploref-orbital contributions in bonding. Combined experimental and computational studies reveal that An(COT^big)₂complexes strongly differ from the previously published coplanar An(COT)₂sandwiches due to the bent geometry and electron-withdrawing nature of the substituents. While COT^bigdisplays comparatively weaker electron donation, the low-energyf-ftransitions in An(COT^big)₂have increased molar absorptivity consistent with the removal of the parity selection rule and better energetic matching between ligand and actinide 5forbitals as the series is traversed. For Pu(COT^big)₂, covalent mixing of donor 5fmetal orbitals and the ligand-π orbitals is especially strong. 

We report the selective electrochemical biphasic capture of the uranyl cation (UO 2 2+ ) from mixed-metal alkali (Cs + ), lanthanide (Nd 3+ , Sm 3+ ), and actinide (Th 4+ , UO 2 2+ ) aqueous solutions to an organic, 1,2-dichloroethane (DCE), phase using the ortho -substituted nido -carborane anion, [1,2-(Ph 2 PO) 2 -1,2-C 2 B 10 H 10 ] 2− (POCb2−). The reduced POCb2− is generated by electrochemical reduction of the closo -carborane, POCb, prior to mixing with the aqueous mixed-metal solution. Subsequent UO 2 2+ release from the captured product, [UO2(POCb)2]2−, was performed by galvanostatic bulk electrolysis of the DCE phase and back-extraction of UO 2 2+ to a fresh aqueous phase. The selective capture and release of UO 2 2+ was confirmed by combined ICP-OES and NMR spectral analyses of the aqueous and organic phases, respectively, against the newly synthesized nido -carborane complexes, [[CoCp*2][Cs(POCb)]]2, [CoCp*2]3[Nd(POCb)3], [CoCp*2]3[Sm(POCb)3], and [CoCp*2]2[Th(POCb)3].