Ad. Richardson et al., Gas-phase molecular structures of third row transition-metal hexafluoridesWF6, ReF6, OsF6, IrF6, and PtF6. An electron-diffraction and ab initio study, INORG CHEM, 39(13), 2000, pp. 2787-2793
The molecular structures of WF6, ReF6, OsF6, IrF6, and PtF6 have been measu
red by electron diffraction from the gases, the last from both PtF6 itself
and from a vapor assumed to consist of a mixture of O-2 and PtF6 obtained b
y heating the salt O2PtF6. For models of O-h symmetry the bond lengths in t
he first three members of the series are essentially identical, but the Ir-
F and Pt-F bonds are respectively about 0.01 and 0.02 Angstrom longer. Mode
ls of D-4h symmetry were also tested for ReF6, OsF6, and IrF6 in which oper
ation of the Jahn-Teller effect is thought possible. For these models the s
ame trend was seen in the average bond-length values. The effect of three-a
tom multiple scattering was also investigated, and experimental estimates o
f the effects of vibrational averaging ("shrinkage") on the distances were
obtained. Normal-coordinate analyses based on the observed wavenumbers yiel
ded stretching force constants consistent with the usual inverse bond-lengt
h/force-constant relationship. Ab initio molecular orbital optimizations of
the molecules constrained to O-h symmetry were carried out at several leve
ls of theory and basis-set size. Less extensive optimizations of ReF6, OsF6
, and IrF6 with D-4h symmetry were also carried out. The best overall agree
ment with both the experimental values and the distance trend for O-h symme
try was obtained with the Hay-Wadt (n+1)VDZ basis on the metals and the aug
-cc-pVTZ on the fluorines at the MP2 level, but these bases with B3P86 and
B3PW91 density functional theory were nearly as good and with B3LYP only sl
ightly worse. The D-4h structures for ReF6, OsF6, and IrF6 with the cited b
ases at the B3P86 level were slightly more stable (respectively 0.8, 2.6, a
nd 1.4 kcal/mol) with the axial bonds shorter by about 0.04 Angstrom in ReF
6 and 0.07 Angstrom in OsF6, but about 0.05 Angstrom longer in IrF6. The si
gnificance of these values is uncertain. The experimental bond lengths (r(g
)/Angstrom) with estimated 2 sigma uncertainties for the models of O-h symm
etry are W-F = 1.829(2), Re-F = 1.829(2), Os-F = 1.828(2), Ir-F = 1.839(2),
and Pt-F = 1.852(2); the Pt-F value from the O2PtF6 sample was 1.851(2) An
gstrom. Although the experimental data neither confirm nor refute the exist
ence of the Jahn-Teller effect in ReF6, OsF6, and IrF6, they ensure that if
present the distortion from O-h symmetry must be small.