0000000000178202
AUTHOR
Stefan Roller
Tetra-p-tolyl-verbindungen p-Tol4Si und p-Tol4Ge: Ein beitrag zur konfiguration der tetraaryl-methan-analoga Ar4M (M = C, Si, Ge, Sn, Pb)
Abstract p-Tol4Si and p-Tol4Ge have been obtained from the reaction of p-TolLi with SiCl4 and of p-TolMgBr with GeCl4, respectively. The crystal structures have been determined and compared with those of the homologous compounds p-Tol4Sn and p-Tol4Pb. The latter two molecules (space group I 4 ) exhibit a S4 axis running between the aromatic groups and are shortened along this axis: all four p-Tol groups are closer together than in an undistorted tetrahedron. In the cases of the silane and germane (space group Pc), the tetrahedron is lengthened along one of the bond axes CM: only three of the four p-Tol groups are closer together, and the set up of a special molecular symmetry is blocked. A…
Kristallstruktur, thermische Ausdehnung und Farbwechsel von (Me3Ge)2Sb-Sb(GeMe3)2 und anderen Distibanen
Abstract Single crystals of the distibanes (Me3M)4Sb2 (1: M = Si, 2: M = Ge) are obtained by the oxidation in air of (Me3M)3Sb. The crystal structure of 2 is reported. 2 forms linear chains of distibane molecules in trans conformation with Sb ··· Sb contacts of 386 pm at −110°C and 390 pm at 22°C. The thermal expansion of crystals of 2 and (Me3Sn)4Sb2 (3) has been determined. UV-VIS spectra of 1–3, Me4Sb2 (4), Et4Sb2 (5), and Ph4Sb2 (6) in different phases have been recorded. The spectra of 1–5 are consistent with the visible colour changes.
Über polygermane
Summary Reaction of LiGePh2GePh3 with Cl2GePh2 at −65°C in ether yields n-Ge5Ph12 as the main product, in addition to shorter-chained polygermanes. The analysis of the resulting products and the isolation of the pentagermane was done by HPLC. The crystal structure was determined (R = 0.095). The conformation of the Ge5 chain is antiperiplanar-anticlinal (−179.3 and +114.4°) with mean Ge-Ge distances of 247.6 (central) and 244.3 pm (terminal).
Über polygermane
Abstract The synthesis of GePh4 and Ge2Ph6 by Grignard reaction in THF or ether/toluene leads to the by-products Ge3Ph8 (up to 11%) and Ge4Ph10 (up to 18%) which is dependant on using an excess of Mg. A quantitative analysis of the resulting products by HPLC and a semipreparative separation by column, flash, and HPL chromatography is described. The crystal structures of Ge3Ph8 (R = 0.075) and Ge4Ph10 · 2C6H6 (R = 0.054) have been determined. Ge4Ph10 has Ci symmetry and both chain conformations are well staggered (49–70° for Ge3Ph8, 53–66° for Ge4Ph10). The GeGe distances and GeGeGe angles are 244 pm and 121° (Ge3Ph8), and 246 pm and 118° (Ge4Ph10).
(Me3Sn)2SbSb(SnMe3)2, 1∞-verknüpfte SbSb-Hanteln in einem thermochromen Distiban mit Schweratomgerüst
Abstract Single crystals of the thermochromic distibane (Me 3 Sn) 4 Sb 2 ( 1 ) are obtained by irradiation of (Me 3 Sn) 3 Sb with sunlight. The crystal structure of 1 is reported as linear chains of distibane molecules in trans conformation with Sb ⋯ Sb contacts of 389 ppm. Diffuse reflexion spectra of 1 in the solid state and in solution demonstrate thermochromic effect. The Raman spectrum of solid 1 exhibits strong absorption at 162 cm −1 for ν(Sb 2 ).