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 ΔG298.15K = 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.
Original language | English |
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Pages (from-to) | 1353-1363 |
Journal | Organometallics |
Volume | 41 |
Issue number | 11 |
Early online date | 18 May 2022 |
DOIs | |
Publication status | Published - 13 Jun 2022 |