Synthesis and Structural Characterization of the First Quaternary Plutonium Thiophosphates:  K₃Pu(PS₄)₂ and APuP₂S₇ (A = K, Rb, Cs)

Abstract

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.

Cs3UP2S8, a Coordination Polymer Containing the Unprecedented [U=S]2+ Sulfidouranium(2+) Moiety

“…More recently, Dorhout and Ibers expanded thiophosphate actinide chemistry to the plutonium thiophosphates K 3 Pu(PS 4 ) 2 and A PuP 2 S 7 ) ( A = K, Rb, Cs)56 and the neptunium compounds57 Np(PS 4 ), Np(P 2 S 6 ) 2 , and A 11 Np 7 (PS 4 ) 13 , ( A = K, Rb),58 which are anologous to Pr(PS 4 ),59 the uranium thiophosphate U(P 2 S 6 ) 2 28 and A 11 U 7 (PS 4 ) 13 , ( A = K, Rb) 45…”

All the Colors of the Rainbow: Diversification of Flower Color and Intraspecific Color Variation in the Genus Iris

“…Red coloration may be a good predictor of bird-pollination in irises, but not vice-versa. There is only one taxon with red flowers, and it is bird-pollinated ( I. fulva , Emms and Arnold, 2000 ; Martin et al, 2008 ), but other bird-pollinated species are not red (e.g., I. missouriensis , Lyon, 1973 ). This suggests that color is likely not the major trait driving pollinator-shifts from insects to birds in Iris .…”

Comprehensive Uranium Thiophosphate Chemistry: Framework Compounds Based on Pseudotetrahedrally Coordinated Central Metal Atoms

“…Still, in the chalcogen-rich systems the chalcogen's ability to catenate has led to formal oxidation state assignments beyond 4+ in Rb 5 U 4 P 4 Se 26 = Rb 4 (U 5+ ) 4 (PSe 4 3-) 4 P(Se 2 2-) 4 (Se 2-) 2 , [11] which are still object of discussion. [12] Whereas binary or ternary uranium (and actinide) chalcogenides [13][14][15][16][17][18][19][20][21][22] and quaternary uranium (and actinide) chalcophosphates A a U x P y Q z , [23][24][25][26][27][28][29][30][31][32] many of which are accessible from reactive polychalcogenide fluxes, [33] are reasonably well characterized, our information concerning the corresponding ternary compounds U x P y Q z is scarce. [34] We have observed in the initial report [35] of the research described herein in full that the tetrahedral network compound U(P 2 S 6 ) 2 is formed by the reaction of U, P 2 S 5 , and S. Herein the uranium atoms are coordinated by the chalcogeno moieties in a pseudotetrahedral manner with thiophosphate groups acting as linear connectors between the central metal atoms.…”