- STRUCTURAL AND THERMODYNAMIC ASPECTS OF AN ELECTRON-DIFFRACTION STUDY ON SATURATED THALLIUM MONOFLUORIDE VAPOR
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A fresh analysis has been performed on the original electron-diffraction data for saturated thallium monofluoride vapor.The diffraction data have been combined with spectroscopic ones to derive the equilibrium geometry and the complete harmonic force fiel
- Girichev, G. V.,Lapshina, S. B.,Giricheva, N. I.
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- Polymorphism of Thallium Pentafluorotellurate (IV), TlTeF//5.
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A colorimetry study of thallium pentafluorotellurate (IV) indicates a reversible phase transition near 192 K. Powder diffraction analysis has been performed for the high and low-temperature forms. Structural data are: form I (298 K): monoclinic system; a equals 14. 099 angstrom, b equals 6. 510 angstrom c equals 11. 864 angstrom, beta equals 91. 03 degree ; form II (123 K): monoclinic system; a equals 14. 218 angstrom, b equals 8. 825 angstrom, c equals 8. 559 angstrom, beta equals 91. 2 degree . These results are discussed in comparison with the thermodynamic characteristics of the I yields II transition.
- Diot, Michel,El Mail, Rachad,Bastide, Jean-Pierre,Nguyen-Ba-Chanh
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- Reactions of 1,2,3,4,5-Pentafluorocyclopentadiene
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The synthesis of 1,2,3,4,5-pentafluorocyclopentadiene (2) from 1,2,3,4,5-pentachloro-1,2,3,4,5-pentafluorocyclopentane (1) is closely investigated.Side-products are 1,2,3,4-tetrafluorocyclopentadiene (4) and 5-chloro-1,2,3,4-tetrafluorocyclopentadiene (5).Under UV irradiation, 2 isomerizes to give 1,2,3,5,5-pentafluorocyclopentadiene (6). 2 dimerizes forming a mixture of Diels-Alder products.This dimerisation is irreversible until 700 deg C.The hydrogen in 2 can be replaced by bromine forming 7. 2 adds Cl2, Br2, I2, and carbonylmetal hydrides.Also with the most stable salt Tl(+)C5F5(-) (8) the synthesis of a η5-C5F5 complex was unsuccessful.A modified synthesis of hexafluorocyclopentadiene (12) from hexachlorocyclopentadiene (9) is presented. 12 adds AsF5 forming c-C5F7AsF4 (13).With SbF5 no cation c-C5F5(+) (14) could be detected so far.
- Paprott, Gerhard,Lehmann, Sabine,Seppelt, Konrad
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p. 727 - 734
(2007/10/02)
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- Matrix-isolation study of oxide-transfer reactions to halogen-containing Lewis acids: Synthesis of the CO2F22- anion and attempted synthesis of the BF3O2- anion
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The oxide-transfer technique has been coupled with matrix isolation in an attempt to synthesize and characterize the BF3O2- and CO2F22- anions, through the reaction of Tl2O with either BF3 or COF2. In the latter experiments, two sets of product bands were observed; one agreed well with the absorptions of the known CO2F- anion. The second set has been assigned to the CO2F22- anion in the matrix-isolated Tl+2CO2F22- triple ion, which rapidly eliminated TlF upon warming to form the Tl+CO2F- anion. Attempts to synthesize the BF3O2- anion in a similar fashion were not successful, suggesting that previous reports of the room-temperature synthesis of this anion are incorrect.
- David, Shelle J.,Ault, Bruce S.
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p. 1238 - 1241
(2008/10/08)
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- Organothallium compounds. VI. Reactions of bromobis(pentafluorophenyl)thallium(III) with main group elements
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Bromobis(pentafluorophenyl)thallium(IlI) reacts with many main group elements on heating in the absence of a solvent to give pentafluorophenyl derivatsves of these elements. The compounds C6F5M (M = Cl, Br, or I), (C6F5)2M (M = Zn, Cd, Hg, S, Se or Te), (C6F5)3M (M = In, P, As, or Sb), and (C6F5)M (M = Ge or Sn) have been prepared by this method. Substantial decomposition of (C6F5)2TlBr occurs on reaction with aluminium, gallium, lead and bismuth, but pcntafluorophenyl derivatives of these elements are not obtained.
- Deacon,Parrott
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p. 287 - 295
(2008/10/08)
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