UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}: A ribbon structure containing a heterobimetallic 5d-5f M{sub 3} cluster

Journal Article · Mon Feb 15 04:00:00 EST 2010 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/j.jssc.2009.10.012· OSTI ID:21372480

Wells, Daniel M; Chan, George H ^[1]; Ellis, Donald E ^[1]

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1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (United States)

A new solid-state compound containing a heterobimetallic cluster of U and Ta, UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}, has been synthesized and its structure has been characterized by single-crystal X-ray diffraction methods. UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6} was synthesized from UCl{sub 4} and Ta{sub 1.2}S{sub 2} at 883 K. The O is believed to have originated in the Ta{sub 1.2}S{sub 2} reactant. The compound crystallizes in the space group P1-bar of the triclinic system. The structure comprises a UTa{sub 2} unit bridged by mu{sub 2}-S{sub 2} and mu{sub 3}-O groups. Each Ta atom bonds to two mu{sub 2}-S{sub 2}, the mu{sub 3}-O, and two terminal Cl atoms. Each U atom bonds to two mu{sub 2}-S{sub 2}, the mu{sub 3}-O, and four Cl atoms. The Cl atoms bridge in pairs to neighboring U atoms to form a ribbon structure. The bond distances are normal and are consistent with formal oxidation states of +IV/+V/-II/-I/-I for U/Ta/O/S/Cl, respectively. The optical absorbance spectrum displays characteristic transition peaks near the absorption edge. Density functional theory was used to assign these peaks to transitions between S{sup 1-} valence-band states and empty U 5f-6d hybrid bands. Density-of-states analysis shows overlap between Ta 5d and U bands, consistent with metal-metal interactions. - The UTa2O(S2)3Cl6 cluster with completed coordination sphere around uranium

• OSTI ID: 21372480
• Journal Information: Journal of Solid State Chemistry, Journal Name: Journal of Solid State Chemistry Journal Issue: 2 Vol. 183; ISSN 0022-4596; ISSN JSSCBI
• Country of Publication: United States
• Language: English

Related Subjects

36 MATERIALS SCIENCE
ABSORPTION
ACTINIDE COMPOUNDS
BOND LENGTHS
CALCULATION METHODS
CHALCOGENIDES
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
CRYSTAL LATTICES
CRYSTAL STRUCTURE
CRYSTALS
DENSITY FUNCTIONAL METHOD
DIFFRACTION
DIMENSIONS
HALIDES
HALOGEN COMPOUNDS
LENGTH
MOLECULAR CLUSTERS
MONOCRYSTALS
REFRACTORY METAL COMPOUNDS
SCATTERING
SORPTION
SPACE GROUPS
SPECTRA
SULFIDES
SULFUR COMPOUNDS
SYMMETRY GROUPS
SYNTHESIS
TANTALUM COMPOUNDS
TEMPERATURE RANGE
TEMPERATURE RANGE 1000-4000 K
TRANSITION ELEMENT COMPOUNDS
TRICLINIC LATTICES
URANIUM CHLORIDES
URANIUM COMPOUNDS
VARIATIONAL METHODS
X-RAY DIFFRACTION