Dithio- and Diselenophosphinate Thorium(IV) and Uranium(IV) Complexes: Molecular and Electronic Structures, Spectroscopy, and Transmetalation Reactivity

We report a comparison of the molecular and electronic structures of dithio- and diselenophosphinate, (E2PR2)1– (E = S, Se; R = iPr, tBu), with thorium­(IV) and uranium­(IV) complexes. For the thorium dithiophosphinate complexes, reaction of ThCl4(DME)2 with 4 equiv of KS2PR2 (R = iPr, tBu) produced the homoleptic complexes, Th­(S2PiPr2)4 (1S-Th-iPr) and Th­(S2PtBu2)4 (2S-Th-tBu). The diselenophosphinate complexes were synthesized in a similar manner using KSe2PR2 to produce Th­(Se2PiPr2)4 (1Se-Th-iPr) and Th­(Se2PtBu2)4 (2Se-Th-tBu). U­(S2PiPr2)4, 1S-U-iPr, could be made directly from UCl4 and 4 equiv of KS2PiPr2. With (Se2PiPr2)1–, using UCl4 and 3 or 4 equiv of KSe2PiPr2 yielded the monochloride product U­(Se2PiPr2)3Cl (3Se-UiPr-Cl), but using UI4(1,4-dioxane)2 produced the homoleptic U­(Se2PiPr2)4 (1Se-U-iPr). Similarly, the reaction of UCl4 with 4 equiv of KS2PtBu2 yielded U­(S2PtBu2)4 (2S-U-tBu), whereas the reaction with KSe2PtBu2 resulted in the formation of U­(Se2PtBu2)3Cl (4Se-UtBu-Cl). Using UI4(1,4-dioxane)2 and 4 equiv of KSe2PtBu2 with UCl4 in acetonitrile yielded U­(Se2PtBu2)4 (2Se-U-tBu). Transmetalation reactions were investigated with complex 2Se-U-tBu and various CuX (X = Br, I) salts to yield U­(Se2PtBu2)3X (6Se-UtBu-Br and 7Se-UtBu-I) and 0.25 equiv of [Cu­(Se2PtBu2)]4 (8Se-Cu-tBu). Additionally, 2Se-U-tBu underwent transmetalation reactions with Hg2F2 and ZnCl2 to yield U­(Se2PtBu2)3F (6) and U­(Se2PtBu2)3Cl (4Se-UtBu-Cl), respectively. The molecular structures were analyzed using 1H, 13C, 31P, and 77Se NMR and IR spectroscopy and structurally characterized using X-ray crystallography. Using the QTAIM approach, the electronic structure of all homoleptic complexes was probed, showing slightly more covalent bonding character in actinide–selenium bonds over actinide–sulfur bonds.