Structures of homoleptic eight- and nine-coordinate uranium(IV) perchlorate complexes with sulfoxide molecules as ligands

Nobuyoshi Koshino, Yoshihiro Kachi, Tamás R. Varga, A. Bényei, Motoo Shiro, Koichiro Takao, Yasuhisa Ikeda

Research output: Contribution to journalArticle

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Abstract

Homoleptic eight- and nine-coordinate U(IV) perchlorate complexes with sulfoxide ligands have been characterized crystallographically. Crystals of [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso (dmso = dimethyl sulfoxide), and [U(tmso)8](ClO4)4 · 2tmso (tmso = tetramethylene sulfoxide) were found to have dodecahedral, tricapped trigonal prismatic, and square antiprismatic geometries, respectively. Average U-O bond distances in [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso, and [U(tmso)8](ClO4)4 · 2tmso are 2.35(3), 2.41 (4), and 2.35(3) Å, respectively. Furthermore, it was found that [U(dmso)8]4+ is in equilibrium with [U(dmso)9]4+ in CH3NO2 solution containing dmso. Thermodynamic parameters for such an equilibrium are as follows: K (25 °C) = 3.4 ± 0.2 dm3 mol-1, ΔH = -54.9 ± 4.5 kJ mol-1, and ΔS = -174 ± 15 J K-1 mol-1.

Original languageEnglish
Pages (from-to)3433-3439
Number of pages7
JournalInorganica Chimica Acta
Volume362
Issue number10
DOIs
Publication statusPublished - Aug 1 2009

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sulfoxide
Uranium
Dimethyl sulfoxide
perchlorates
uranium
Ligands
Thermodynamics
Crystals
ligands
Molecules
Geometry
molecules
thermodynamics
geometry
crystals
Dimethyl Sulfoxide
perchlorate

Keywords

  • Crystal structure
  • Eight- and nine-coordination
  • Equilibrium reaction
  • Homoleptic complexes
  • Sulfoxide
  • Uranium(IV)

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Structures of homoleptic eight- and nine-coordinate uranium(IV) perchlorate complexes with sulfoxide molecules as ligands. / Koshino, Nobuyoshi; Kachi, Yoshihiro; Varga, Tamás R.; Bényei, A.; Shiro, Motoo; Takao, Koichiro; Ikeda, Yasuhisa.

In: Inorganica Chimica Acta, Vol. 362, No. 10, 01.08.2009, p. 3433-3439.

Research output: Contribution to journalArticle

Koshino, Nobuyoshi ; Kachi, Yoshihiro ; Varga, Tamás R. ; Bényei, A. ; Shiro, Motoo ; Takao, Koichiro ; Ikeda, Yasuhisa. / Structures of homoleptic eight- and nine-coordinate uranium(IV) perchlorate complexes with sulfoxide molecules as ligands. In: Inorganica Chimica Acta. 2009 ; Vol. 362, No. 10. pp. 3433-3439.
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abstract = "Homoleptic eight- and nine-coordinate U(IV) perchlorate complexes with sulfoxide ligands have been characterized crystallographically. Crystals of [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso (dmso = dimethyl sulfoxide), and [U(tmso)8](ClO4)4 · 2tmso (tmso = tetramethylene sulfoxide) were found to have dodecahedral, tricapped trigonal prismatic, and square antiprismatic geometries, respectively. Average U-O bond distances in [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso, and [U(tmso)8](ClO4)4 · 2tmso are 2.35(3), 2.41 (4), and 2.35(3) {\AA}, respectively. Furthermore, it was found that [U(dmso)8]4+ is in equilibrium with [U(dmso)9]4+ in CH3NO2 solution containing dmso. Thermodynamic parameters for such an equilibrium are as follows: K (25 °C) = 3.4 ± 0.2 dm3 mol-1, ΔH = -54.9 ± 4.5 kJ mol-1, and ΔS = -174 ± 15 J K-1 mol-1.",
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AU - Koshino, Nobuyoshi

AU - Kachi, Yoshihiro

AU - Varga, Tamás R.

AU - Bényei, A.

AU - Shiro, Motoo

AU - Takao, Koichiro

AU - Ikeda, Yasuhisa

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N2 - Homoleptic eight- and nine-coordinate U(IV) perchlorate complexes with sulfoxide ligands have been characterized crystallographically. Crystals of [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso (dmso = dimethyl sulfoxide), and [U(tmso)8](ClO4)4 · 2tmso (tmso = tetramethylene sulfoxide) were found to have dodecahedral, tricapped trigonal prismatic, and square antiprismatic geometries, respectively. Average U-O bond distances in [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso, and [U(tmso)8](ClO4)4 · 2tmso are 2.35(3), 2.41 (4), and 2.35(3) Å, respectively. Furthermore, it was found that [U(dmso)8]4+ is in equilibrium with [U(dmso)9]4+ in CH3NO2 solution containing dmso. Thermodynamic parameters for such an equilibrium are as follows: K (25 °C) = 3.4 ± 0.2 dm3 mol-1, ΔH = -54.9 ± 4.5 kJ mol-1, and ΔS = -174 ± 15 J K-1 mol-1.

AB - Homoleptic eight- and nine-coordinate U(IV) perchlorate complexes with sulfoxide ligands have been characterized crystallographically. Crystals of [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso (dmso = dimethyl sulfoxide), and [U(tmso)8](ClO4)4 · 2tmso (tmso = tetramethylene sulfoxide) were found to have dodecahedral, tricapped trigonal prismatic, and square antiprismatic geometries, respectively. Average U-O bond distances in [U(dmso)8](ClO4)4 · 0.75CH3NO2, [U(dmso)9](ClO4)4 · 4dmso, and [U(tmso)8](ClO4)4 · 2tmso are 2.35(3), 2.41 (4), and 2.35(3) Å, respectively. Furthermore, it was found that [U(dmso)8]4+ is in equilibrium with [U(dmso)9]4+ in CH3NO2 solution containing dmso. Thermodynamic parameters for such an equilibrium are as follows: K (25 °C) = 3.4 ± 0.2 dm3 mol-1, ΔH = -54.9 ± 4.5 kJ mol-1, and ΔS = -174 ± 15 J K-1 mol-1.

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