Gas-phase electron-diffraction (GED) data together with results from ab initio molecular orbital and normal coordinate calculations have been used to determine the structures of the aluminum trihalides AlX3 (X = Cl, Br, I) and the chloride and bromide dimers Al2Cl6 and Al2Br6. No monomeric species were detected in the vapors of Al2Cl6 at the experimental temperature of 150 °C, nor in Al2Br6 at167 °C, but the vapors of AlCl3 at 400 °C and AlBr3 at 330 °C contained respectively 29 (3)% and 7 (4)% dimer and the AlI3 at 300 °C about 8% I2. The known equilibrium symmetry of the dimers is D 2 h , but the molecules have a very low-frequency, large-amplitude, ring-puckering mode that lowers the thermal average symmetry to C 2 v . The effect of this large-amplitude mode on the interatomic distances was handled by dynamic models of the structures which consisted of a set of pseudoconformers spaced at even intervals along the ring-puckering angle 2Φ. The ring-puckering potential was assumed to be V(Φ) = V 4 0Φ4 + V 2 0Φ2, and the individual pseudoconformers were given Boltzmann weights. The structures were defined in terms of the geometrically consistent r α space constraining the differences between corresponding bond distances and bond angles in the different pseudoconformers to values obtained from ab initio calculations at the HF/6-311G(d) level. Results for the principal distances (r g/Å), angles (∠α,θ/deg), and potential constants (V i 0/kcal mol deg-1) from the combined GED/ab initio study for Al2Cl6/Al2Br6 with estimated 2σ uncertainties are Al−Xb = 2.250(3)/2.433(7), Al−Xt = 2.061(2)/2.234(4), XbAlXb = 90.0(8)/91.6(6), XtAlXt = 122.1(31)/122.1(31), 〈θ〉 = 180 − 2Φ = 165.5(59)/158.2(91), V 4 0 = 0.0/75.0 (assumed), V 2 0 = 25.0/0.0 (assumed). The potential constants could not be refined; although the single-term values listed provide good fits, in each case combinations of quadratic and quartic terms also worked well. For the monomers AlCl3, AlBr3, and AlI3 (D 3 h symmetry assumed in r α space) the distances (r g/Å) with estimated 2σ uncertainties are Al−Cl = 2.062(3), Al−Br = 2.221(3), and Al−I = 2.459(5) Å. Vibrational force fields were evaluated for all molecules. The experimental, theoretical, and vibrational results are discussed.

No abstract

Gas electron diffraction data of (CH3)6Sn2 and (CH3)2Te2 are consistent with molecular models of D3 and C2 symmetry and bond distances Sn–Sn = 277.6(3) pm and Te–Te = 268.6(3) pm, respectively.

No abstract

No abstract