High coordination number actinide-noble gas complexes; a computational study

Abstract

The geometries, electronic structures and bonding of early actinide-noble gas complexes are studied computationally by density functional and wavefunction theory methods, and by ab initio molecular dynamics. AcHe(18)3+ is confirmed...

Photolysis-driven bond activation by thorium and uranium tetraosmate polyhydride complexes

“…38 bridging hydrides around the thorium center, matching the highest observed coordination number around an atom in an isolated compound; 40,41 interestingly, higher coordination numbers have been proposed for early actinide-noble gas complexes. 42 This is reminiscent of the 15-coordinate aminodiboranate thorium complex reported by Girolami, which also features thorium with an extraordinarily large number of bridging hydrides, in this case provided by borohydride-based ligands rather than transition metal polyhydrides. 23 Complex 2-U crystallizes in the cubic space group Pa 3, with a single osmate moiety centered on the 3-fold symmetry axis and another which generates the remaining three osmate fragments through symmetry.…”

Computational study of the interactions of tetravalent actinides (An = Th–Pu) with the α-Fe13 Keggin cluster

“…34,56,59 The magnitude of q ( M ) calculated with QTAIM is higher than that of NPA analysis; such differences have been observed previously. 59,60 The Mulliken and QTAIM charges are in good agreement, decreasing from Th–Pu, and follow n excess (f) in suggesting increased covalency from Th–Pu. Another quantity we have considered is the difference between the atomic number ( Z ) and localisation index ( λ ) derived from the QTAIM.…”

Construction of the Largest Metal-Centered Double-Ring Tubular Boron Clusters Based on Actinide Metal Doping

“…29 However, despite the fact that various metal-doped boron clusters have been extensively studied theoretically and experimentally, boron clusters doped with actinide metal atoms (An) are limited until now. 30 Similar to other metal atoms, doping with actinides can improve the stability of boron clusters, and these clusters exhibit a variety of geometrical structures. For example, the half sandwich structures AnB 12 (An = Th to Cm), 31 the actinide endohedral borospherenes An@B n (An = U and Th; n = 36, 38, and 40), 32,33 the chiral actinide endohedral borospherenes (Ac@B 39 , [Ac@B 39 ] 2+ , and Th@B 39 , [Th@B 39 ] 3+ ), 34 and the actinide-centered borane An(BH) 24 (An = Th to Cm) 35 An@B 20 .…”

“…However, despite the fact that various metal-doped boron clusters have been extensively studied theoretically and experimentally, boron clusters doped with actinide metal atoms (An) are limited until now . Similar to other metal atoms, doping with actinides can improve the stability of boron clusters, and these clusters exhibit a variety of geometrical structures.…”