Heteroleptic actinocenes: a thorium(iv)-cyclobutadienyl-cyclooctatetraenyl-di-potassium-cyclooctatetraenyl complex.

Despite the vast array of η n -carbocyclic C5-8 complexes reported for actinides, cyclobutadienyl (C4) remain exceedingly rare, being restricted to six uranium examples. Here, overcoming the inherent challenges of installing highly reducing C4-ligands onto actinides when using polar starting materials such as halides, we report that reaction of [Th(η8-C8H8)2] with [K2{C4(SiMe3)4}] gives [{Th(η4-C4[SiMe3]4)(μ-η8-C8H8)(μ-η2-C8H8)(K[C6H5Me]2)}2{K(C6H5Me)}{K}] (1), a new type of heteroleptic actinocene. Quantum chemical calculations suggest that the thorium ion engages in π- and δ-bonding to the η4-cyclobutadienyl and η8-cyclooctatetraenyl ligands, respectively. Furthermore, the coordination sphere of this bent thorocene analogue is supplemented by an η2-cyclooctatetraenyl interaction, which calculations suggest is composed of σ- and π-symmetry donations from in-plane in- and out-of-phase C[double bond, length as m-dash]C 2p-orbital combinations to vacant thorium 6d orbitals. The characterisation data are consistent with this being a metal-alkene-type interaction that is integral to the bent structure and stability of this complex.