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Thorium-ligand multiple bonds via reductive deprotection of a trityl group.
- Author(s): Smiles, Danil E;
- Wu, Guang;
- Kaltsoyannis, Nikolas;
- Hayton, Trevor W
- et al.
Published Web Location
https://doi.org/10.1039/c5sc01248aAbstract
Reaction of [Th(I)(NR2)3] (R = SiMe3) (2) with KECPh3 (E = O, S) affords the thorium chalcogenates, [Th(ECPh3)(NR2)3] (3, E = O; 4, E = S), in moderate yields. Reductive deprotection of the trityl group from 3 and 4 by reaction with KC8, in the presence of 18-crown-6, affords the thorium oxo complex, [K(18-crown-6)][Th(O)(NR2)3] (6), and the thorium sulphide complex, [K(18-crown-6)][Th(S)(NR2)3] (7), respectively. The natural bond orbital and quantum theory of atoms-in-molecules approaches are employed to explore the metal-ligand bonding in 6 and 7 and their uranium analogues, and in particular the relative roles of the actinide 5f and 6d orbitals.
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