title: 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.
abstract: 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.
authors.affiliation: Institut für Anorganische Chemie, Technische Universität Graz, Stremayrgasse 16, Austria. s.masters@ed.ac.uk
authors.forename: Margit
authors.initials: M
authors.lastname: Hölbling
authors.forename: Sarah L
authors.initials: SL
authors.lastname: Masters
authors.forename: Michaela
authors.initials: M
authors.lastname: Flock
authors.forename: Judith
authors.initials: J
authors.lastname: Baumgartner
authors.forename: Karl
authors.initials: K
authors.lastname: Hassler
authors.forename: Heather E
authors.initials: HE
authors.lastname: Robertson
authors.forename: Derek A
authors.initials: DA
authors.lastname: Wann