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

Abstract

We report a comparison of the molecular and electronic structures of dithio- and diselenophosphinate, (E2PR2)(1-) (E = S, Se; R = (i)Pr, (t)Bu), with thorium(IV) and uranium(IV) complexes. For the thorium dithiophosphinate complexes, reaction of ThCl4(DME)2 with 4 equiv of KS2PR2 (R = (i)Pr, (t)Bu) produced the homoleptic complexes, Th(S2P(i)Pr2)4 (1S-Th-(i)Pr) and Th(S2P(t)Bu2)4 (2S-Th-(t)Bu). The diselenophosphinate complexes were synthesized in a similar manner using KSe2PR2 to produce Th(Se2P(i)Pr2)4 (1Se-Th-(i)Pr) and Th(Se2P(t)Bu2)4 (2Se-Th-(t)Bu). U(S2P(i)Pr2)4, 1S-U-(i)Pr, could be made directly from UCl4 and 4 equiv of KS2P(i)Pr2. With (Se2P(i)Pr2)(1-), using UCl4 and 3 or 4 equiv of KSe2P(i)Pr2 yielded the monochloride product U(Se2P(i)Pr2)3Cl (3Se-U(iPr)-Cl), but using UI4(1,4-dioxane)2 produced the homoleptic U(Se2P(i)Pr2)4 (1Se-U-(i)Pr). Similarly, the reaction of UCl4 with 4 equiv of KS2P(t)Bu2 yielded U(S2P(t)Bu2)4 (2S-U-(t)Bu), whereas the reaction with KSe2P(t)Bu2 resulted in the formation of U(Se2P(t)Bu2)3Cl (4Se-U(tBu)-Cl). Using UI4(1,4-dioxane)2 and 4 equiv of KSe2P(t)Bu2 with UCl4 in acetonitrile yielded U(Se2P(t)Bu2)4 (2Se-U-(t)Bu). Transmetalation reactions were investigated with complex 2Se-U-(t)Bu and various CuX (X = Br, I) salts to yield U(Se2P(t)Bu2)3X (6Se-U(tBu)-Br and 7Se-U(tBu)-I) and 0.25 equiv of [Cu(Se2P(t)Bu2)]4 (8Se-Cu-(t)Bu). Additionally, 2Se-U-(t)Bu underwent transmetalation reactions with Hg2F2 and ZnCl2 to yield U(Se2P(t)Bu2)3F (6) and U(Se2P(t)Bu2)3Cl (4Se-U(tBu)-Cl), respectively. The molecular structures were analyzed using (1)H, (13)C, (31)P, and (77)Se 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.