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DOI: 10.1039/A604314C (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1997, 1013-1018

Molecular structures of the sixth period metal pentachlorides, MCl5 (M = Ta, W or Re), determined by gas electron diffraction; is Jahn–Teller distortion of WCl5 quenched by spin–orbit coupling?

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Knut Faegri Jr., Arne Haaland, Kjell-Gunnar Martinsen, Tor G. Strand, Hans Vidar Volden, Ole Swang, Carlaxel Anderson, Christina Persson, Sandra Bogdanovic and Wolfgang A. Herrmann

Abstract

The molecular structure of TaCl5 has been optimised under D3h symmetry by density-functional theory calculations. Calculation of the molecular force field and vibrational frequencies showed that the optimised structure corresponds to a minimum on the full potential energy surface. Gas electron diffraction data of MCl5 (M = Ta, W or Re), recorded with nozzle temperatures ranging from 130 to 210 °C, showed that WCl5 and ReCl5 are trigonal bipyramidal like TaCl5. Structure refinements based on molecular models of D3h symmetry lead to satisfactory agreement between experimental and calculated intensities for each compound and yield the M–Cl bond distances (ax/eq): Ta 231.3(5)/226.6(4); W 229.1(4)/224.1(5); Re 226.2(12)/223.7(7) pm. Tungsten pentachloride is a d1 compound and might have exhibited dynamic or static Jahn–Teller distortion from D3h symmetry; it has been suggested that such distortion is quenched by strong spin–orbit coupling.

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