Three new phases in the K/Cu/Th/S system: KCuThS3, K2Cu2ThS4, and K3Cu3Th2S7.

Synthetic exploration of K/Cu/Th/S quaternary phase space has yielded three new compounds: KCuThS3 (I), K2Cu2ThS4 (II), and K3Cu3Th2S7 (III). All three phases are semiconductors with optical band gaps of 2.95, 2.17, and 2.49 eV(I-III). Compound I crystallizes in the orthorhombic space group Cmcm with a = 4.076(1) A, b = 13.864(4) A, and c = 10.541(3) A. Compound II crystallizes in the monoclinic space group C2/m with a = 14.522(1) A, b = 4.026(3) A, and c = 7.566(6) A; beta = 109.949(1) degrees . Compound III crystallizes in orthorhombic space group Pbcn with a = 4.051(2) A, b = 14.023(8) A, and c = 24.633(13) A. The compounds are all layered materials, with each layer composed of threads of edge-sharing ThS6 octahedra bridged by CuS4 tetrahedral threads of varying dimension. The layers are separated by well-ordered potassium ions. The relatively wide range of optical band gaps is attributed to the extent of the CuS4 motifs. As the dimension of the CuS4 chains increases, band gaps decrease in the series. All materials were characterized by single-crystal X-ray diffraction, microprobe chemical analysis, and diffuse reflectance spectroscopy (NIR-UV).

Synthesis and characterization of two quaternary thorium chalcophosphates: Cs4Th2P6S18 and Rb7Th2P6Se21.

Two new thorium chalcophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction, diffuse reflectance, and Raman spectroscopy: Cs4Th2P6S18 (I); Rb7Th2P6Se21 (II). Compound I crystallizes as colorless blocks in the triclinic space group P1 (No. 2) with a = 12.303(4) A, b = 12.471(4) A, c = 12.541(4) A, alpha = 114.607(8) degrees, beta = 102.547(6) degrees, gamma = 99.889(7) degrees, and Z = 2. The structure consists of (Th2P6S18)(4-) layers separated by layers of cesium cations and only contains the (P2S6)(4-) building block. Compound II crystallizes as red blocks in the triclinic space group P1 (No. 2) with a = 11.531(3) A, b = 12.359(4) A, c = 16.161(5) A, alpha = 87.289(6) degrees, beta = 75.903(6) degrees, gamma = 88.041(6) degrees, and Z = 2. The structure consists of linear chains of (Th2P6Se21)(7-) separated by rubidium cations. Compound II contains both the (PSe4)(3-) and (P2Se6)(4-) building blocks. Both structures may be derived from two known rare earth structures where a rare earth site is replaced by an alkali or actinide metal to form these novel structures. Optical band gap measurements show that compound I has a band gap of 2.8 eV and compound II has a band gap of 2.0 eV. Solid-state Raman spectroscopy of compound I shows the vibrations expected for the (P2S6)(4-) unit. Raman spectroscopy of compound II shows the vibrations expected for both (PSe4)(3-) and (P2Se6)(4-) units. Our work shows the remarkable diversity of the actinide chalcophosphate system and demonstrates the phase space is still ripe to discover new structures.

Synthesis and characterization of AU2Se6 (A = K, Cs).

Two new ternary uranium selenides, AU(2)Se(6) (A = K, Cs), were prepared using the reactive flux method. Single crystal X-ray diffraction was performed on single crystals. The compounds crystallize in the orthorhombic Immm space group, Z = 2. CsU(2)Se(6) has cell parameters of a = 4.046(2) A, b = 5.559(3) A, and c = 24.237(12) A. KU(2)Se(6) has cell parameters of a = 4.058(3) A, b = 5.556(4) A, and c = 21.710(17) A. The compounds are isostructural to the previously reported KTh(2)Se(6). The two-dimensional layered structure is related to ZrSe(3) with the alkali metals residing in the interlayer space. The oxidation states of uranium and selenium were evaluated using X-ray photoelectron spectroscopy (XPS). Uranium was found to be tetravalent, while selenium was found to be in two oxidation states, one of which is -2. The other oxidation state is similar to that found in a polyselenide network. While this structure is known, our work examines how the structure changes through the transactinide series.

Higher order speciation effects on plutonium L(3) X-ray absorption near edge spectra.

Pu L(3) X-ray near edge absorption spectra for Pu(0-VII) are reported for more than 60 chalcogenides, chlorides, hydrates, hydroxides, nitrates, carbonates, oxy-hydroxides, and other compounds both as solids and in solution, and substituted in zirconolite, perovskite, and borosilicate glass. This large database extends the known correlations between the energy and shape of these spectra from the usual association of the XANES with valence and site symmetry to higher order chemical effects. Because of the large number of compounds of these different types, a number of novel and unexpected behaviors are observed, such as effects resulting from the medium and disorder that can be as large as those from valence.

Low-temperature synthesis of uranium tetraboride by solid-state metathesis reactions.

A novel synthesis of uranium tetraboride (UB(4)) by solid-state metathesis reaction is demonstrated. This approach significantly lowers the temperature required to synthesize this material to < or = 850 degrees C. When UCl(4) is reacted with 2 equiv of MgB(2) at 850 degrees C, crystalline UB(4) is formed. Powder X-ray diffraction and ICP-AES data support the reduction of UCl(4) to UCl(3) as the initial step in the reaction. The UB(4) product is purified by washing with water.

Chloroheptakis(dimethyl sulfoxide)uranium(IV) trichloride.

In the title complex, [UCl(C(2)H(6)OS)(7)]Cl(3), the uranium metal center is coordinated in a distorted bicapped trigonal prism geometry by seven O atoms from dimethyl sulfoxide ligands and by a terminal chloride ligand. Charge balance is maintained by three outer-sphere chloride ions per uranium(IV) metal center. Principle bond lengths include U-O 2.391 (2)-2.315 (2) A, U-Cl 2.7207 (9) A, and average S-O 1.540 (5) A.

Synthesis and structural characterization of the first quaternary plutonium thiophosphates: K(3)Pu(PS(4))(2) and APuP(2)S(7) (A = K, Rb, Cs).

The first quaternary plutonium metal thiophosphates have been synthesized by the reactive flux method and characterized by single-crystal X-ray diffraction: K(3)Pu(PS(4))(2) (I), KPuP(2)S(7) (II), RbPuP(2)S(7) (III), and CsPuP(2)S(7) (IV). All four compounds crystallize in the monoclinic space group P2(1)/c with Z = 4. Compound I has cell parameters of a = 9.157(1) A, b = 16.866(2) A, c = 9.538(1), and beta = 90.610(3)degrees. Compound II has cell parameters of a = 9.641(1) A, b = 12.255(1) A, c = 9.015(1) A, and beta = 90.218(1)degrees. Compound III has cell parameters of a = 9.8011(6) A, b = 12.3977(7) A, c = 9.0263(5) A, and beta = 90.564(1)degrees. Compound IV has cell parameters of a = 10.1034(7) A, b = 12.5412(9) A, c = 9.0306(6) A, and beta = 91.007(1)degrees. Compound I is isostructural to a family of rare-earth metal thiophosphates and comprises bicapped trigonal prismatic PuS(8) polyhedra linked in chains through edge-sharing interactions and through thiophosphate tetrahedra. Compounds II-IV crystallize in a known structure type not related to any previously observed actinide thiophosphates and contain the (P(2)S(7))(4-) corner-shared bitetrahedral ligand as a structural building block. A summary of important bond distances and angles for these new plutonium thiophosphate materials is compared to the limited literature on plutonium solid-state compounds. Diffuse reflectance spectra confirm the Pu(III) oxidation state and Raman spectroscopy confirms the tetrahedral PS(4)(3-) building block in all structures.

Synthesis, Structure, and Reactivity of 1,2-(1',1',2',2'-Tetramethyldisilane-1',2')carborane.

The novel strained compound 1,2-(1',1',2',2'-tetramethyldisilane-1',2')carborane (1) was synthesized by the reaction of 1,2-dilithiocarborane and dichlorotetramethyldisilane. Compound 1 was characterized by solution methods and its structure determined by single-crystal X-ray diffraction. In contrast to its organic analogue o-(disilanyl)phenylene, the reaction of 1 with ethanol leads to cleavage of a Si-C bond rather than a Si-Si bond. Similarly to other cyclic disilanes, exposure of a solution of 1 to oxygen leads to the insertion of an oxygen atom into the Si-Si bond. The structure of the oxygen inserted product was also determined by X-ray crystallography. The general chemistry and attempts at polymerizing 1 are briefly discussed.

Electrochemical Properties of Bis(dicarbollide)uranium Dibromide.

The cyclic voltammogram of [(eta(5)-C(2)B(9)H(11))(2)UBr(2)].2[Li(THF(4))] shows the electrochemical generation of a uranium(III) species. Subsequent Na/Hg reduction of [(eta(5)-C(2)B(9)H(11))(2)UBr(2)].2[Li(THF(4))] leads to the new isolable uranium(III) species [(eta(5)-C(2)B(9)H(11))(2)UBr(THF)].2[Li(THF)(x)()] (x = 2-4). The green uranium(III) complex was characterized by NMR and elemental analysis and its structure determined by single-crystal X-ray crystallography. The coordination geometry around the dinegative uranium(III) moiety is pseudotetrahedral with two dicarbollide ligands, a bromide ligand, and a THF ligand. The electrochemical properties of the dicarbollide complex are discussed and compared to similar cyclopentadienyluranium complexes.