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

Abstract

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 withmore » metal-metal interactions. - The UTa2O(S2)3Cl6 cluster with completed coordination sphere around uranium« less

Authors:
;  [1];  [1]
  1. Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 (United States)
Publication Date:
OSTI Identifier:
21372480
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 183; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2009.10.012; PII: S0022-4596(09)00494-0; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ABSORPTION; BOND LENGTHS; DENSITY FUNCTIONAL METHOD; MOLECULAR CLUSTERS; MONOCRYSTALS; SPACE GROUPS; SPECTRA; SULFIDES; SYNTHESIS; TANTALUM COMPOUNDS; TEMPERATURE RANGE 1000-4000 K; TRICLINIC LATTICES; URANIUM CHLORIDES; X-RAY DIFFRACTION; ACTINIDE COMPOUNDS; CALCULATION METHODS; CHALCOGENIDES; CHLORIDES; CHLORINE COMPOUNDS; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; CRYSTALS; DIFFRACTION; DIMENSIONS; HALIDES; HALOGEN COMPOUNDS; LENGTH; REFRACTORY METAL COMPOUNDS; SCATTERING; SORPTION; SULFUR COMPOUNDS; SYMMETRY GROUPS; TEMPERATURE RANGE; TRANSITION ELEMENT COMPOUNDS; URANIUM COMPOUNDS; VARIATIONAL METHODS

Citation Formats

Wells, Daniel M, Chan, George H, Ellis, Donald E, Department of Physics and Astronomy, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, and Ibers, James A., E-mail: ibers@chem.northwestern.ed. UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}: A ribbon structure containing a heterobimetallic 5d-5f M{sub 3} cluster. United States: N. p., 2010. Web. doi:10.1016/j.jssc.2009.10.012.
Wells, Daniel M, Chan, George H, Ellis, Donald E, Department of Physics and Astronomy, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, & Ibers, James A., E-mail: ibers@chem.northwestern.ed. UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}: A ribbon structure containing a heterobimetallic 5d-5f M{sub 3} cluster. United States. doi:10.1016/j.jssc.2009.10.012.
Wells, Daniel M, Chan, George H, Ellis, Donald E, Department of Physics and Astronomy, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113, and Ibers, James A., E-mail: ibers@chem.northwestern.ed. Mon . "UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}: A ribbon structure containing a heterobimetallic 5d-5f M{sub 3} cluster". United States. doi:10.1016/j.jssc.2009.10.012.
@article{osti_21372480,
title = {UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}: A ribbon structure containing a heterobimetallic 5d-5f M{sub 3} cluster},
author = {Wells, Daniel M and Chan, George H and Ellis, Donald E and Department of Physics and Astronomy, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208-3113 and Ibers, James A., E-mail: ibers@chem.northwestern.ed},
abstractNote = {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},
doi = {10.1016/j.jssc.2009.10.012},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 2,
volume = 183,
place = {United States},
year = {2010},
month = {2}
}