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Thorium-ligand multiple bonds via reductive deprotection of a trityl group.


ABSTRACT: 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.

SUBMITTER: Smiles DE 

PROVIDER: S-EPMC5707506 | biostudies-literature | 2015 Jul

REPOSITORIES: biostudies-literature

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Thorium-ligand multiple bonds <i>via</i> reductive deprotection of a trityl group.

Smiles Danil E DE   Wu Guang G   Kaltsoyannis Nikolas N   Hayton Trevor W TW  

Chemical science 20150430 7


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

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