Thorium- and Uranium-Mediated C-H Activation of a Silyl-Substituted Cyclobutadienyl Ligand.

ABSTRACT: Cyclobutadienyl complexes of the f-elements are a relatively new yet poorly understood class of sandwich and half-sandwich organometallic compounds. We now describe cyclobutadienyl transfer reactions of the magnesium reagent [(η⁴-Cb'''')Mg(THF)₃] (1), where Cb'''' is tetrakis(trimethylsilyl)cyclobutadienyl, toward thorium(IV) and uranium(IV) tetrachlorides. The 1:1 stoichiometric reactions between 1 and AnCl₄ proceed with intact transfer of Cb'''' to give the half-sandwich complexes [(η⁴-Cb'''')AnCl(μ-Cl)₃Mg(THF)₃] (An = Th, 2; An = U, 3). Using a 2:1 reaction stoichiometry produces [Mg₂Cl₃(THF)₆][(η⁴-Cb'''')An(η³-C₄H(SiMe₃)₃-κ-(CH₂SiMe₂)(Cl)] (An = Th, [Mg₂Cl₃(THF)₆][4]; An = U [Mg₂Cl₃(THF)₆][5]), in which one Cb'''' ligand has undergone cyclometalation of a trimethylsilyl group, resulting in the formation of an An-C σ-bond, protonation of the four-membered ring, and an η³-allylic interaction with the actinide. Complex solution-phase dynamics are observed with multinuclear nuclear magnetic resonance spectroscopy for both sandwich complexes. A computational analysis of the reaction mechanism leading to the formation of 4 and 5 indicates that the cyclobutadienyl ligands undergo C-H activation across the actinide center.

SUBMITTER: Tsoureas N 

PROVIDER: S-EPMC9768750 | biostudies-literature | 2022 Dec

REPOSITORIES: biostudies-literature