Impact of Noncovalent Interactions on the Structural Chemistry of Thorium(IV)-Aquo-Chloro Complexes

Five novel tetravalent thorium (Th) compounds that consist of Th(H 2 O) x Cl y structural units were isolated from acidic aqueous solutions using a series of nitrogen-containing heterocyclic hydrogen (H) bond donors. Taken together with three previously reported phases, the compounds provide a series of monomeric Th IV complexes wherein the effects of noncovalent interactions (and H-bond donor identity) on Th structural chemistry can be examined. Seven distinct structural units of the general formulas [Th(H 2 O) x Cl 8- x ] x -4 ( x = 2, 4) and [Th(H 2 O) x Cl 9- x ] x -5 ( x = 5-7) are described. The complexes range from chloride-deficient [Th(H 2 O) 7 Cl 2 ] 2+ o chloride-rich [Th(H 2 O) 2 Cl 6 ] 2- species, and theory was used to understand the relative energies that separate complexes within this series via the stepwise chloride addition to an aquated Th cation. Electronic structure theory predicted the reaction energies of chloride addition and release of water through a series of transformations, generally highlighting an energetic driving force for chloride complexation. To probe the role of the counterion in the stabilization of these complexes, electrostatic potential (ESP) surfaces were calculated. The ESP surfaces indicated a dependence of the chloride distribution about the Th metal center on the p K a of the countercation, highlighting the directing effects of noncovalent interactions (e.g., Hbonding) on Th speciation.