Addition of KSCPh3 to [U(NR2)3] (R = SiMe3) in tetrahydrofuran, followed by addition of 18-crown-6, results in formation of the U(IV) sulfide, [K(18-crown-6)][U(S)(NR2)3] (1) and Gomberg's dimer. Similarly, addition of KOCPh3 to [U(NR2)3] in tetrahydrofuran, followed by addition of 18-crown-6, results in formation of the U(IV) oxide, [K(18-crown-6)][U(O)(NR2)3] (3). Also observed in this transformation are the triphenylmethyl anion, [K(18-crown-6)(THF)2][CPh3] (5), and the U(IV) alkoxide, [U(OCPh3)(NR2)3] (4).
Reaction of [Th(I)(NR2)3] (R = SiMe3) (1) with 1 equiv of either [K(18-crown-6)]2[Se4] or [K(18-crown-6)]2[Te2] affords the thorium dichalcogenides, [K(18-crown-6)][Th(η(2)-E2)(NR2)3] (E = Se, 2; E = Te, 3), respectively. Removal of one chalcogen atom via reaction with Et3P, or Et3P and Hg, affords the monoselenide and monotelluride complexes of thorium, [K(18-crown-6)][Th(E)(NR2)3] (E = Se, 4; E = Te, 5), respectively. Both 4 and 5 were characterized by X-ray crystallography and were found to feature the shortest known Th-Se and Th-Te bond distances. The electronic structure and nature of the actinide-chalcogen bonds were investigated with (77)Se and (125)Te NMR spectroscopy accompanied by detailed quantum-chemical analysis. We also recorded the (77)Se NMR shift for a U(VI) oxo-selenido complex, [U(O)(Se)(NR2)3](-) (δ((77)Se) = 4905 ppm), which features the highest frequency (77)Se NMR shift yet reported, and expands the known (77)Se chemical shift range for diamagnetic substances from ∼3300 ppm to almost 6000 ppm. Both (77)Se and (125)Te NMR chemical shifts of given chalcogenide ligands were identified as quantitative measures of the An-E bond covalency within an isoelectronic series and supported significant 5f-orbital participation in actinide-ligand bonding for uranium(VI) complexes in contrast to those involving thorium(IV). Moreover, X-ray diffraction studies together with NMR spectroscopic data and density functional theory (DFT) calculations provide convincing evidence for the actinide-chalcogen multiple bonding in the title complexes. Larger An-E covalency is observed in the [U(O)(E)(NR2)3](-) series, which decreases as the chalcogen atom becomes heavier.
Reductive deprotection of the trityl group from [Th(ECPh3)(NR2)3] (E = O, S), by reaction with KC8, in the presence of 18-crown-6, affords the thorium oxo complex, [K(18-crown-6)][Th(O)(NR2)3], and the thorium sulphide complex, [K(18-crown-6)][Th(S)(NR2)3], respectively.
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