A repeat electron diffraction study on the structures of WCl3, W2Cl6, and WCl4

The gas phase structures of tungsten chlorides: density functional theory calculations on WCl6, WCl5, WCl4, WCl3 and W2Cl6 †

“…13 Least-squares refinement yielded an average bond distance of W-Cl 226.9(3) pm and an angle between the pseudo-axial ligands of about 180Њ. 12 These results are clearly in disagreement with those of our calculations.…”

“…The dimer was found to have a diborane-like structure of D 2h symmetry, [WCl 2 (µ-Cl)] 2 . 12 Our DFT calculations on singlet electronic states led to the identification of two stationary points on the potential energy surface of W 2 Cl 6 , one corresponding to a diborane-like structure similar to that suggested by EK, the other corresponding to an ethane-like, metal-metal bonded structure of D 3d symmetry. See Table 1.…”

“…The mean W-Cl bond distance was found to be 224.7(3) pm, the angle spanned by the pseudo-axial ligands was about 150Њ, and the angle spanned by the pseudo-equatorial ligands about 90Њ. 12 This structure is surprising. All monomeric tetrahalides of the Group 4 metals as well as the d 2 tetrafluorides CrF 4 and MoF 4 have been found to be tetrahedral in the gas phase.…”

Structure and Other Molecular Properties of Actinide Trichlorides AnCl3 (An = Th–Cm)

“…We note, however, that the experimental data originate from a time when assistance from quantum chemical calculations was not yet available. Particularly the missing reliable vibrational data may call for a larger experimental uncertainty than that given by Bazhanov et al , …”

“…We start with UCl 3 , for which molecule both experimental and quantum chemical results have been reported. The molecular geometry has been determined by gas electron diffraction at 800 K by Bazhanov et al , The molecule was reported to have a strongly pyramidal structure ( C 3 v symmetry, bond angle 95 ± 3°). From the vibrational amplitudes derived at the analysis of the electron diffraction data the authors estimated the fundamental frequencies.…”