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f-Element Half-Sandwich Complexes: A Tetrasilylcyclobutadienyl-Uranium(IV)-Tris(tetrahydroborate) Anion Pianostool
Josef T Boronski1, Laurence R Doyle1, John A Seed1
1Department of Chemistry and Centre for Radiochemistry Research, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Abstract:
Despite there being numerous examples of f-element compounds supported by cyclopentadienyl, arene, cycloheptatrienyl, and cyclooctatetraenyl ligands (C5-8 ), cyclobutadienyl (C4 ) complexes remain exceedingly rare. Here, we report that reaction of [Li2 {C4 (SiMe3 )4 }(THF)2 ] (1) with [U(BH4 )3 (THF)2 ] (2) gives the pianostool complex [U{C4 (SiMe3 )4 }(BH4 )3 ][Li(THF)4 ] (3), where use of a borohydride and preformed C4 -unit circumvents difficulties in product isolation and closing a C4 -ring at uranium. Complex 3 is an unprecedented example of an f-element half-sandwich cyclobutadienyl complex, and it is only the second example of an actinide-cyclobutadienyl complex, the other being an inverse-sandwich. The U-C distances are short (av. 2.513 Å), reflecting the formal 2- charge of the C4 -unit, and the SiMe3 groups are displaced from the C4 -plane, which we propose maximises U-C4 orbital overlap. DFT calculations identify two quasi-degenerate U-C4 π-bonds utilising the ψ2 and ψ3 molecular orbitals of the C4 -unit, but the potential δ-bond using the ψ4 orbital is vacant.
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