Mesoionic Carbene Complexes of Uranium(IV) and Thorium(IV).

ABSTRACT: We report the synthesis and characterization of uranium(IV) and thorium(IV) mesoionic carbene complexes [An{N(SiMe₃)₂}₂(CH₂SiMe₂NSiMe₃){MIC}] (An = U, 4U and Th, 4Th; MIC = {CN(Me)C(Me)N(Me)CH}), which represent rare examples of actinide mesoionic carbene linkages and the first example of a thorium mesoionic carbene complex. Complexes 4U and 4Th were prepared via a C-H activation intramolecular cyclometallation reaction of actinide halides, with concomitant formal 1,4-proton migration of an N-heterocyclic olefin (NHO). Quantum chemical calculations suggest that the An-carbene bond comprises only a σ-component, in contrast to the uranium(III) analogue [U{N(SiMe₃)₂}₃(MIC)] (1) where computational studies suggested that the 5f³ uranium(III) ion engages in a weak one-electron π-backbond to the MIC. This highlights the varying nature of actinide-MIC bonding as a function of actinide oxidation state. In solution, 4Th exists in equilibrium with the Th(IV) metallacycle [Th{N(SiMe₃)₂}₂(CH₂SiMe₂NSiMe₃)] (6Th) and free NHO (3). The thermodynamic parameters of this equilibrium were probed using variable-temperature NMR spectroscopy yielding an entropically favored but enthalpically endothermic process with an overall reaction free energy of ΔG _298.15K = 0.89 kcal mol^-1. Energy decomposition analysis (EDA-NOCV) of the actinide-carbon bonds in 4U and 4Th reveals that the former is enthalpically stronger and more covalent than the latter, which accounts for the respective stabilities of these two complexes.

SUBMITTER: Seed JA 

PROVIDER: S-EPMC9490841 | biostudies-literature | 2022 Jun

REPOSITORIES: biostudies-literature