Systematic Investigation of Thorium(IV)– and Uranium(IV)–Ligand Bonding in Dithiophosphonate, Thioselenophosphinate, and Diselenophosphonate Complexes
datasetposted on 16.09.2013 by Andrew C. Behrle, Charles L. Barnes, Nikolas Kaltsoyannis, Justin R. Walensky
Datasets usually provide raw data for analysis. This raw data often comes in spreadsheet form, but can be any collection of data, on which analysis can be performed.
Homoleptic soft-donor actinide complexes of the general form An[E2PROR′]4 were synthesized from salt metathesis between ThCl4(DME)2 or UI4(1,4-dioxane)2 and M[E2PROR′], M = Na, K, to yield 2 (An = Th, E = S, R = 4-MeOC6H4, R′ = Me), 3 (An = Th, E = S, R = 4-MeOC6H4, R′ = tBu), 4 (An = U, E = S, R = 4-MeOC6H4, R′ = Me), 5 (An = Th, E = Se, R = C6H5, R′ = Me), and 6 (An = U, E = Se, R = C6H5, R′ = Me). In addition thorium and uranium thioselenophosphinate complexes 7 and 8 were produced from the reaction of ThCl4(DME)2 and UI4(1,4-dioxane)2 and Na[SSePPh2], respectively. All compounds were characterized using elemental analysis, 1H and 31P NMR, and IR spectroscopy, and the U(IV) compounds were also examined with UV–vis spectroscopy. The 77Se NMR spectrum of 5 reveals the first reported resonance with a Th–Se bond. The solid-state structures of 2, 5, 7, and 8 were determined by X-ray crystallography. The actinide–ligand bonding was examined using density functional theory calculations in conjunction with quantum theory of atoms-in-molecules analysis and shows slightly increased covalency in actinide–selenium bonds than actinide–sulfur.