Thorium–ligand multiple bonds via reductive deprotection of a trityl group

Reaction of [Th(I)(NR(2))(3)] (R = SiMe(3)) (2) with KECPh(3) (E = O, S) affords the thorium chalcogenates, [Th(ECPh(3))(NR(2))(3)] (3, E = O; 4, E = S), in moderate yields. Reductive deprotection of the trityl group from 3 and 4 by reaction with KC(8), in the presence of 18-crown-6, affords the thorium oxo complex, [K(18-crown-6)][Th(O)(NR(2))(3)] (6), and the thorium sulphide complex, [K(18-crown-6)][Th(S)(NR(2))(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.