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

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      Publication Details (including relevant citation   information):

        Department of Chemistry, University of Missouri, Columbia, Missouri     65211-7600, United States 
        Department of Chemistry, Lancaster University, Lancaster LA1 4YB,     United Kingdom 
        Inorg. Chem., 2015, 54 (24), pp 11625–11636  
        DOI: 10.1021/acs.inorgchem.5b01342  


      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.

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