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

Abstract

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.

Thorium–phosphorus triamidoamine complexes containing Th–P single- and multiple-bond interactions

“…However, to be verified this hypothesis requires a greater range of complexes to be prepared and compared, but progress in thorium-ligand multiple bonding pales when compared with uranium. For example, under ambient conditions there are only a handful of each class of structurally authenticated formal Th=C carbene134445, Th=N imido464748 and terminal Th=O oxo or Th=E···K (E=O, S, Se, Te) complexes495051 known; where thorium–phosphorus multiple bonds are concerned, they are conspicuous by their absence outside of cryogenic matrix isolation experiments52. Indeed, of fewer than thirty crystallographically authenticated thorium–phosphorus complexes in the Cambridge Structural Database53 seven are phosphanides54555657585960, three are polyphosphides6162, one is a phosphinidiide54, a term we use to indicate its bridging nature, and the remainder are phosphine derivatives; a dithorium-phosphinidiide complex [{Th(η 5 -C 5 Me 5 ) 2 (OMe)} 2 (μ-PH)] (ref.…”

Should environmental effects be included when performing QTAIM calculations on actinide systems? A comparison of QTAIM metrics for Cs2UO2Cl4, U(Se2PPh2)4 and Np(Se2PPh2)4 in gas phase, COSMO and PEECM

“…This is due partly to the experimental difficulties associated with obtaining high quality experimental electron densities on radioactive systems featuring very heavy elements, and partly a function of the QTAIM only recently being extended to quantum chemical studies of the actinide elements. Indeed, we were the first group to extensively employ the QTAIM in this capacity, and have used it to study both covalency [6][7][8][9][10][11][12][13][14][15][16][17][18] and bond strength [19][20][21] in a range of molecular f element systems.…”

Formation of a Ce(IV) Oxo Complex via Inner Sphere Nitrate Reduction

“…Herein, we describe the synthesis and characterization of a rare cerium oxo complex. 29 and have here applied the same approach to the fictitious Ce analogue of these systems, and to complex 1. The bond lengths between the Ce and ligating atoms in the latter are well reproduced computationally, with the largest difference between experiment and theory being < 0.06 Å (for the Ce-O bond, which is slightly overestimated by DFT).…”

“…In all cases NBO finds the M-O interaction to be a  + 2 triple bond, and the compositions of the  natural localised molecular orbitals (NLMOs) are given in 29 .…”