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Issue 13, 2010

The structures of tellurium(iv) halides in the gas phase and as solvated molecules

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Abstract

The structures of molecular tellurium tetrafluoride and tellurium tetrachloride were determined by a combination of gas-phase electron diffraction, mass spectrometry and quantum chemical calculations. The combined GED/MS experiments showed no evidence of decomposition of TeF4 and TeCl4. No ions of oligomeric (dimeric, trimeric, etc.) or any other composition were found in the mass spectra. The monomeric molecules possess a pseudo trigonal bipyramidal structure (C2v symmetry) with the equatorial Te–X distances being shorter than the axial ones. The fluorine atoms are bent away from the lone pair resulting in XeqTe–Xeq and XeqTe–Xax bond angles smaller than 120 and 90°, respectively. The structure of solvates TeF4 (THF)2, TeF4 (dioxane) TeF4 (DME)2, TeF4(Et2O) TeF4(toluene), TeCl4(CH3CN)2, TeCl4(DME)2 and TeCl4(dioxane) were determined by X-ray diffraction. The structures of tellurium tetrafluoride solvates are strongly influenced by the choice of the solvent molecules. Monomeric TeF4 units were obtained with THF, DME and dioxane whereas fluoride bridged coordination polymers were formed using diethyl ether or toluene. All tellurium tetrachloride solvates studied contain monomeric TeCl4 units with coordinated solvent molecules. Coordination numbers range from four in the gas phase to eight in the TeF4 dimethoxyethane solvate. Geometric parameters of the TeX4 molecules in the crystal, solvates and gas phase were compared. DFT, MP2, CCSD, CCSD(T) methods were applied for calculation of geometric and vibrational characteristics of free TeX4 molecules (X = F, Cl). The pseudorotation barriers were estimated and an NBO analysis was performed. It was shown that both, GED and theoretical, quantitative results are in agreement with the qualitative results of the VSEPR model.

Graphical abstract: The structures of tellurium(iv) halides in the gas phase and as solvated molecules

Supplementary files

Article information


Submitted
27 Oct 2009
Accepted
06 Jan 2010
First published
08 Feb 2010

Dalton Trans., 2010,39, 3245-3255
Article type
Paper

The structures of tellurium(IV) halides in the gas phase and as solvated molecules

S. A. Shlykov, N. I. Giricheva, A. V. Titov, M. Szwak, D. Lentz and G. V. Girichev, Dalton Trans., 2010, 39, 3245 DOI: 10.1039/B922474B

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