Molecular structure of 1,2-bis(trifluoromethyl)-1,1,2,2-tetramethyldisilane in the gas, liquid, and solid phases: unusual conformational changes between phases.

The molecular structure of 1,2-bis(trifluoromethyl)-1,1,2,2-tetramethyldisilane has been determined in three different phases (solid, liquid, and gas) using various spectroscopic and diffraction techniques. Both the solid-state and gas-phase investigations revealed only one conformer to be present in the sample analyzed, whereas the liquid phase revealed the presence of three conformers. The data have been reproduced using computational methods and a rationale is presented for the observation of three conformers in the liquid state.

Molecular structures of the digermanes Me2XGeGeXMe2 (X = Me, Cl, and H): an ab initio study combined with experimental investigation by Raman spectroscopy and gas electron diffraction.

Ab initio calculations were carried out to investigate the potential-energy surface for internal rotation of the methylated digermanes hexamethyldigermane Me(3)GeGeMe(3) ( 1), dichlorotetramethyldigermane Me(2)ClGeGeClMe(2) ( 2), and tetramethyldigermane Me(2)HGeGeHMe(2) ( 3). Different basis sets [6-31+G(d), SDD, aug-cc-pVTZ] were employed at the DFT and MP2 levels of theory to optimize structures and to calculate energies and vibrational frequencies. For 1, one minimum representing a staggered structure was located on the potential-energy surface. For 2 and 3, antiperiplanar conformations with C 2 symmetry were found to be the global minima. Additionally, synclinal minima were located for 2 and 3 when certain basis sets were employed. Determination of structural parameters in the gas phase by gas electron diffraction confirmed the computed predictions for all three compounds. For 2 and 3, the ratios of antiperiplanar to synclinal conformer were detected to be 90:10 (328 K) and 72:28 (293 K), respectively, by gas electron diffraction. The experimentally determined GeGe bond lengths in 1, 2, and 3 in the gas phase are 241.4(1), 242.7(2) (averaged for antiperiplanar and synclinal), and 241.7(1) pm (equal for antiperiplanar and synclinal). Only averaged structures were observed, using Raman spectroscopy, for 2 and 3 because the wavenumber differences are small between conformers and there is only a small contribution from the second conformer in each case. For 2, the crystal structure was also determined by X-ray diffraction. An anticlinal structure (with Cl atoms eclipsing the C atoms) was found with a GeGe bond length of 242.1 pm.

Supersilyl radicals from the dissociation of superdisilane observed by gas electron diffraction.

The vapour produced upon mild heating of hexa-tert-butyldisilane (superdisilane) has been studied by gas electron diffraction and ab initio molecular orbital calculations; the disilane is not observed in the vapour, and the observed radical structure is not the lowest energy structure predicted ab initio.

The cyclohexasilanes Si6H11X and Si6Me11X with X=F, Cl, Br and I: a quantum chemical and Raman spectroscopic investigation of a multiple conformer problem.

The conformers of the monohalocyclohexasilanes, Si(6)H(11)X (X=F, Cl, Br or I) and the haloundecamethylcyclohexasilanes, Si(6)Me(11)X (X=F, Cl, Br or I) are investigated by DFT calculations employing the B3LYP density functional and 6-31+G* basis sets for elements up to the third row, and SDD basis sets for heavier elements. Five minima are found for Si(6)H(11)X-the axial and equatorial chair conformers, with the substituent X either in an axial or equatorial position-and another three twisted structures. The equatorial chair conformer is the global minimum for the X=Cl, Br and I, the axial chair for X=F. The barrier for the ring inversion is approximately 13 kJ mol(-1) for all four compounds. Five minima closely related to those of Si(6)H(11)X are found for Si(6)Me(11)X. Again, the equatorial chair is the global minimum for X=Cl, Br and I, and the axial chair for X=F. Additionally, two symmetrical boat conformers are found as local minima on the potential energy surfaces for X=F, Cl and Br, but not for X=I. The barrier for the ring inversion is approximately 14-16 kJ mol(-1) for all compounds. The conformational equilibria for Si(6)Me(11)X in toluene solution are investigated using temperature dependent Raman spectroscopy. The wavenumber range of the stretching vibrations of the heavy atoms X and Si from 270-370 cm(-1) is analyzed. Using the van't Hoff relationship, the enthalpy differences between axial and equatorial chair conformers (H(ax-)H(eq.)) are 1.1 kJ mol(-1) for X=F, and 1.8 to 2.8 kJ mol(-1) for X=Cl, Br and I. Due to rapid interconversion, only a single Raman band originating from the "averaged" twist and boat conformers could be observed. Generally, reasonable agreement between the calculated relative energies and the experimentally determined values is found.