In search of tris(trimethylsilylcyclopentadienyl) thorium

Reduction of Cp'₃ThCl, Cp'₃ThBr, and Cp'₃ThI (Cp' = C₅H₄SiMe₃) with potassium graphite generates dark blue solutions with reactivity and spectroscopic properties consistent with the formation of Cp'₃Th. The EPR and UV-visible spectra of the solutions are similar to those of crystallographically-characterized tris(cyclopentadienyl) Th(iii) complexes: [C₅H₃(SiMe₃)₂]₃Th, (C₅Me₄H)₃Th, (C₅^tBu₂H₃)₃Th, and (C₅Me₅)₃Th. Density functional theory (DFT) analysis indicates that the UV-visible spectrum is consistent with Cp'₃Th and not [Cp'₃ThBr]^1-. Although single crystals of Cp'₃Th have not been isolated, the blue solution reacts with Me₃SiCl, I₂, and HC[triple bond, length as m-dash]CPh to afford products expected from Cp'₃Th, namely, Cp'₃ThCl, Cp'₃ThI, and Cp'₃Th(C[triple bond, length as m-dash]CPh), respectively. Reactions with MeI give mixtures of Cp'₃ThI and Cp'₃ThMe. Evidence for further reduction of the blue solutions to a Cp'-ligated Th(ii) complex has not been observed. The crystal structures of Cp'₃ThMe and (Cp'₃Th)₂(μ-O) were also determined as part of these studies.