Andrew C. Behrle

Formation of a Bridging Phosphinidene Thorium Complex.

The synthesis and structural determination of the first thorium phosphinidene complex are reported. The reaction of 2 equiv of (C5Me5)2Th(CH3)2 with H2P(2,4,6-(i)Pr3C6H2) at 95 °C produces [(C5Me5)2Th]2(μ2-P[(2,6-CH2CHCH3)2-4-(i)PrC6H2] as well as 4 equiv of methane, 2 equiv from deprotonation of the phosphine and 2 equiv from C-H bond activation of one methyl group of each of the isopropyl groups at the 2- and 6-positions. Transition state calculations indicate that the steps in the mechanism are P-H, C-H, C-H, and then P-H bond activation to form the phosphinidene.

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 = (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.

Uranium(III) and thorium(IV) alkyl complexes as potential starting materials

The synthesis and characterisation of a rare U(iii) alkyl complex, U[η4-Me2NC(H)C6H5]3, using the dimethylbenzylamine (DMBA) ligand has been accomplished. While attempting to prepare the U(iv) compound, reduction to the U(iii) complex occurred. In the analogous Th(iv) system, C-H bond activation of a methyl group of one dimethylamine was observed yielding Th[η4-Me2NC(H)C6H5]2[η5-(CH2)MeNC(H)C6H5] with a dianionic DMBA ligand. The utility of these complexes as starting materials has been analyzed using a bulky dithiocarboxylate ligand to yield tetravalent actinide species.

Coordination Chemistry and QTAIM Analysis of Homoleptic Dithiocarbamate Complexes, M(S2CNiPr2)4 (M = Ti, Zr, Hf, Th, U, Np)

In a systematic approach to comparing the molecular structure and bonding in homoleptic transition-metal and actinide complexes, a series of dithiocarbamates, M(S2CNiPr2)4 (M = Ti, Zr, Hf, Th, U, Np), have been synthesized. These complexes have been characterized through spectroscopic and X-ray crystallographic analysis, and their bonding has been examined using density functional theory calculations. Computational results indicate that the covalent character associated with the M-S bonds shows the trend of Hf < Zr < Th < Ti < U ≈ Np.

Structure and properties of [(4,6-tBu2C6H2O)2Se]2An(THF)2, An = U, Np, and their reaction with p-benzoquinone

The synthesis and characterization of U(iv) and Np(iv) selenium bis(phenolate) complexes are reported. The reaction of two equivalents of the U(iv) complex with p-benzoquinone results in the formation of a U(v)-U(v) species with a bridging reduced quinone. This represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex.