The nature of bis(cyclopentadienyl)uranium dichloride and cyclopentadienyluranium trichloride in solution and in the solid state

Richard D. Ernst, William J. Kennelly, Cynthia Secaur Day, Tobin J Marks, Tobin J. Marks

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Abstract

The composition of the compound "(C5H5)2UCl2", prepared from uranium tetrachloride and thallium cyclopentadienide in DME (1,2-dimethoxyethane), has been investigated in the solid state by infrared spectroscopy and X-ray powder diffraction, and in solution by electronic and 1H NMR spectroscopy. All results indicate that (C5H5)2UCl2 is a mixture of the known compounds (C5H5)3UCl and (C5H5)UCl3(DME). The structure of this latter species is proposed to be mer pseudooctahedral on the basis of solution NMR studies (which also show it to be stereochemically dynamic) and by analogy to the related complex, (CH3C5H4)UCl3(THF)2, the solid-state molecular structure of which has been determined using single-crystal X-ray diffraction techniques. This compound crystallizes in the monoclinic space group P21/n with four molecules in a cell of dimensions a = 10.481 (2) Å, b = 12.981 (2) Å, c = 13.834 (2) Å, and β = 105.86 (1)°. Least-squares refinement of the 181 variables led to a value for the conventional R index (on F) of 0.058 for 3698 independent reflections having 2θMoKᾱ <60.4° and I > 3σr(I). The coordination geometry about the uranium ion is approximately mer octahedral with the η5-CH3C5H4 and one coordinated TH F occupying trans axial positions, and the other THF and three chlorine atoms occupying equatorial positions. The U-C(cyclopentadienyl), U-Cl, and U-O distances average 2.720 (14), 2.623 (3), and 2.450 (8) Å, respectively. The principal distortion of the coordination geometry from octahedral is a 0.47-Å displacement of the uranium atom out of the equatorial plane toward the cyclopentadienyl ring. It is found that the THF ligands of (C5H5)UCl3(THF)2 are readily displaced by nitrogenous bases such as 2,2′-bipyridyl and 1,10-phenanthroline.

Original languageEnglish
Pages (from-to)2656-2664
Number of pages9
JournalJournal of the American Chemical Society
Volume101
Issue number10
Publication statusPublished - 1979

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Uranium
X-Ray Diffraction
Powder Diffraction
Atoms
2,2'-Dipyridyl
Thallium
Geometry
Chlorine
Molecular Structure
Least-Squares Analysis
X ray powder diffraction
Molecular structure
Nuclear magnetic resonance spectroscopy
Infrared spectroscopy
Spectrum Analysis
Magnetic Resonance Spectroscopy
Ligands
Nuclear magnetic resonance
Single crystals
Ions

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The nature of bis(cyclopentadienyl)uranium dichloride and cyclopentadienyluranium trichloride in solution and in the solid state. / Ernst, Richard D.; Kennelly, William J.; Day, Cynthia Secaur; Marks, Tobin J; Marks, Tobin J.

In: Journal of the American Chemical Society, Vol. 101, No. 10, 1979, p. 2656-2664.

Research output: Contribution to journalArticle

Ernst, Richard D. ; Kennelly, William J. ; Day, Cynthia Secaur ; Marks, Tobin J ; Marks, Tobin J. / The nature of bis(cyclopentadienyl)uranium dichloride and cyclopentadienyluranium trichloride in solution and in the solid state. In: Journal of the American Chemical Society. 1979 ; Vol. 101, No. 10. pp. 2656-2664.
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abstract = "The composition of the compound {"}(C5H5)2UCl2{"}, prepared from uranium tetrachloride and thallium cyclopentadienide in DME (1,2-dimethoxyethane), has been investigated in the solid state by infrared spectroscopy and X-ray powder diffraction, and in solution by electronic and 1H NMR spectroscopy. All results indicate that (C5H5)2UCl2 is a mixture of the known compounds (C5H5)3UCl and (C5H5)UCl3(DME). The structure of this latter species is proposed to be mer pseudooctahedral on the basis of solution NMR studies (which also show it to be stereochemically dynamic) and by analogy to the related complex, (CH3C5H4)UCl3(THF)2, the solid-state molecular structure of which has been determined using single-crystal X-ray diffraction techniques. This compound crystallizes in the monoclinic space group P21/n with four molecules in a cell of dimensions a = 10.481 (2) {\AA}, b = 12.981 (2) {\AA}, c = 13.834 (2) {\AA}, and β = 105.86 (1)°. Least-squares refinement of the 181 variables led to a value for the conventional R index (on F) of 0.058 for 3698 independent reflections having 2θMoKᾱ <60.4° and I > 3σr(I). The coordination geometry about the uranium ion is approximately mer octahedral with the η5-CH3C5H4 and one coordinated TH F occupying trans axial positions, and the other THF and three chlorine atoms occupying equatorial positions. The U-C(cyclopentadienyl), U-Cl, and U-O distances average 2.720 (14), 2.623 (3), and 2.450 (8) {\AA}, respectively. The principal distortion of the coordination geometry from octahedral is a 0.47-{\AA} displacement of the uranium atom out of the equatorial plane toward the cyclopentadienyl ring. It is found that the THF ligands of (C5H5)UCl3(THF)2 are readily displaced by nitrogenous bases such as 2,2′-bipyridyl and 1,10-phenanthroline.",
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N2 - The composition of the compound "(C5H5)2UCl2", prepared from uranium tetrachloride and thallium cyclopentadienide in DME (1,2-dimethoxyethane), has been investigated in the solid state by infrared spectroscopy and X-ray powder diffraction, and in solution by electronic and 1H NMR spectroscopy. All results indicate that (C5H5)2UCl2 is a mixture of the known compounds (C5H5)3UCl and (C5H5)UCl3(DME). The structure of this latter species is proposed to be mer pseudooctahedral on the basis of solution NMR studies (which also show it to be stereochemically dynamic) and by analogy to the related complex, (CH3C5H4)UCl3(THF)2, the solid-state molecular structure of which has been determined using single-crystal X-ray diffraction techniques. This compound crystallizes in the monoclinic space group P21/n with four molecules in a cell of dimensions a = 10.481 (2) Å, b = 12.981 (2) Å, c = 13.834 (2) Å, and β = 105.86 (1)°. Least-squares refinement of the 181 variables led to a value for the conventional R index (on F) of 0.058 for 3698 independent reflections having 2θMoKᾱ <60.4° and I > 3σr(I). The coordination geometry about the uranium ion is approximately mer octahedral with the η5-CH3C5H4 and one coordinated TH F occupying trans axial positions, and the other THF and three chlorine atoms occupying equatorial positions. The U-C(cyclopentadienyl), U-Cl, and U-O distances average 2.720 (14), 2.623 (3), and 2.450 (8) Å, respectively. The principal distortion of the coordination geometry from octahedral is a 0.47-Å displacement of the uranium atom out of the equatorial plane toward the cyclopentadienyl ring. It is found that the THF ligands of (C5H5)UCl3(THF)2 are readily displaced by nitrogenous bases such as 2,2′-bipyridyl and 1,10-phenanthroline.

AB - The composition of the compound "(C5H5)2UCl2", prepared from uranium tetrachloride and thallium cyclopentadienide in DME (1,2-dimethoxyethane), has been investigated in the solid state by infrared spectroscopy and X-ray powder diffraction, and in solution by electronic and 1H NMR spectroscopy. All results indicate that (C5H5)2UCl2 is a mixture of the known compounds (C5H5)3UCl and (C5H5)UCl3(DME). The structure of this latter species is proposed to be mer pseudooctahedral on the basis of solution NMR studies (which also show it to be stereochemically dynamic) and by analogy to the related complex, (CH3C5H4)UCl3(THF)2, the solid-state molecular structure of which has been determined using single-crystal X-ray diffraction techniques. This compound crystallizes in the monoclinic space group P21/n with four molecules in a cell of dimensions a = 10.481 (2) Å, b = 12.981 (2) Å, c = 13.834 (2) Å, and β = 105.86 (1)°. Least-squares refinement of the 181 variables led to a value for the conventional R index (on F) of 0.058 for 3698 independent reflections having 2θMoKᾱ <60.4° and I > 3σr(I). The coordination geometry about the uranium ion is approximately mer octahedral with the η5-CH3C5H4 and one coordinated TH F occupying trans axial positions, and the other THF and three chlorine atoms occupying equatorial positions. The U-C(cyclopentadienyl), U-Cl, and U-O distances average 2.720 (14), 2.623 (3), and 2.450 (8) Å, respectively. The principal distortion of the coordination geometry from octahedral is a 0.47-Å displacement of the uranium atom out of the equatorial plane toward the cyclopentadienyl ring. It is found that the THF ligands of (C5H5)UCl3(THF)2 are readily displaced by nitrogenous bases such as 2,2′-bipyridyl and 1,10-phenanthroline.

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