Über Tetraaryl-methan-analoga in der gruppe 14

The title compounds have been synthesized by Li and Grignard reactions. The crystal structure of Ph3Si-p-Tol has been determined. The substitution of only one phenyl by one p-tolyl group causes only a slight deviation from the ideal S4 symmetry of Ph4Si. Gradual replacement of phenyl by p-tolyl groups leads to increasing low field shifts for all 13C(ipso) atoms. The substitution of the first phenyl group by p-tolyl in Ph4Si and Ph4Sn results in a high field shift both for δ(29Si) (−0.3 ppm) and for δ(119Sn) (−1 ppm). Further replacement shows nearly linear dependencies (Δδ(29Si) = −0.1 ppm, Δδ(119Sn) = + 1.5 ppm per p-tolyl group).

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 CM: only three of the four p-Tol groups are closer together, and the set up of a special molecular symmetry is blocked. A…

ChemInform Abstract: Mixed Group 14-Group 14 Bonds. Part 5. Six Perphenylated Propane Analogues Ph3M-M′Ph2-M′′Ph3 (M, M′, M′′: Si/Ge): Electronegativity Differences Between Silicon and Germanium.

ChemInform Abstract: Tetraarylmethane Analogues in Group 14. Part 2. Ph4-nSi(p-Tol)n and Ph4-nSn(p-Tol)n (n = 0-4): Effect of the p-Tolyl Substituents on Structure and NMR Chemical Shifts.

Tetraaryl-methane analogues in group 14—V. Distortion of tetrahedral geometryin terms of through-space π–π and π–σ interactions andNMR sagging in terms of π–σcharge transfer

Abstract 44 members of thecompound series Ph4−nMRn (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph3Sn (o-Tol) and PhSn (o-Tol)3 were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space π–π repulsion and π–σ attraction leads to either elongated or compressed tetrahedral geometry. 29 Si-, 119 Sn- and 207 Pb-NMR chemical shifts were determined in solution and in the solid state.73 Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a π–σcharge transfer which is constrained by…

Über gemischte gruppe 14-gruppe 14-bindungen

Abstract The six title compounds have been synthesized from Li/KSi/GePh 3 and chloride precursors in THF, DME or diethyl ether at low temperature. The six compounds crystallize isomorphously in the space group Pbca with ordered arrangement for the four symmetrical cases (SiSi 2.394, SiGe 2.412, GeGe 2.440 A) and statistical alignment for the two asymmetrical chains; angle range 116.5–123.3°. Replacement of Si by Ge atoms leads to low field NMR chemical shifts for 13 C ipso atoms and for directly bonded 29 Si atoms. This is in accordance with an enhanced electronegativity of germanium in comparison with silicon. UV/Vis and IR/Raman data are given.