Molecular structures of the sixth period metal pentachlorides,MCl5 (M = Ta, W or Re), determined by gaselectron diffraction; is Jahn–Teller distortion of WCl5quenched by spin–orbit coupling?
1997
The molecular structure of TaCl
5
has been optimised under
D
3h
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
MCl
5
(M = Ta, W or Re), recorded with nozzle
temperatures ranging from 130 to 210 °C, showed that
WCl
5
and ReCl
5
are trigonal bipyramidal like
TaCl
5
. Structure refinements based on molecular models of
D
3h
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
d
1
compound and might have exhibited dynamic or static
Jahn–Teller distortion from D
3h
symmetry; it has been suggested that such distortion is quenched by
strong spin–orbit coupling.
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