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.
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher.
To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b01342
