0000000000810340
AUTHOR
Andrea Zickgraf
showing 5 related works from this author
Tetraaryl-methane analogues in group 14—V. Distortion of tetrahedral geometryin terms of through-space π–π and π–σ interactions andNMR sagging in ter…
1998
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…
As(III)/Sb(III)/Bi(III)–halide distances and stretching vibrations. An application of the Varshni relationship upon hypervalent group 15 compounds
1998
Abstract A Varshni treatment between stretching frequencies and bond lengths is given for 16 heterocycles of the types Hal–M(SCH 2 CH 2 ) 2 X and Hal–M(CH 2 CH 2 CH 2 ) 2 X (M=As/Sb/Bi, Hal=Cl/Br/I, X=O, S, NR). The intensities of the Raman emissions for the M–Hal bonds increase in the following order: Cl≪Br −1/2 , decrease in the following order: Cl>Br≫I. Practically, the Varshni constants are used to estimate the complementary quantity, stretching frequency or bond length, in 35 cases.
Nucleophilic attack within Ge, Sn and Pb complexes containing Me2N(CH2)(3) - as a potential intramolecular donor ligand
1998
Abstract Thirteen tin compounds LxPhySnClz and LPh2SnPhX (x=1–4, y=0–3, z=0–2, XPh, F, Cl, Br, I, OPh), six germanium compounds LxPhyGeClz and four lead compounds LPh2PbPhX (XPh, Cl, Br, I) containing the potential intramolecular donor LMe2N(CH2)3—have been synthesized by Grignard reactions, redistribution, halogenation, exchange of halide and phenylation. Evidence for 1,5-chelation in which the donor Me2N intramolecularly attacks the Lewis-acidic atoms Ge, Sn or Pb is provided by six crystal structure determinations: Me2N(CH2)3SnPh2Cl, 5; Me2N(CH2)3SnPh2Br, 5a; Me2N(CH2)3SnPh2I, 5b; Me2N(CH2)3SnPh2OPh, 5d; Me2N(CH2)3SnPh3·HCl·H2O. 1a; Me2N(CH2)3PbPh2I, 17b), and by solution 13C, 119Sn a…
Heterocyclic systems containing tin(IV)—XIII [1]. Possible ceasing or inversion of the structuraltrans influence during the course of a bimolecular n…
1997
Abstract In the series of the heterocycles X[(CH2)3]2SnR2 (16 newly synthesized compounds and two taken from the literature) and in the germanium analog BuiN[(CH2)3]2GeCl2, the donor group X (= NMe, NBz, NBui, NPri, O, S) intramolecularly attacks the Lewis acidic atoms Sn or Ge. Eight structure determinations (and, in addition, 2 taken from the literature) are compared. The nucleophilic attack at Sn is stronger for the ligands R2 =Cl2 than for the more electronegative R2 = (OSiPh3)2. Overall the familiartrans influence holds: simultaneous approach of X and weakening of the ligand R (trans). In three cases of subtly graded donor strength a slight inversion or ceasing is observed: shorter dis…
Heterocyclic systems containing antimony (III) -VIII . Hypervalency by intramolecular 1,5-chelation Sb · · · N in rings RSb [ (CH2) 3] 2NR′ (NR′ = NM…
1998
Abstract Eleven antimony compounds RSb [ (CH2) 3] 2 NR′ and eight germanium compounds R2Ge [ (CH2) 3] 2 NR′ (some combinations of R = Cl, I, NCS, OSiPh3, Ph, and NR′ = NMe, NBz, NBui) have been synthesized by diGrignard reactions and subsequent treatment with AgSCN, Ph3SiONa or PhLi. The compounds were compared to 14 Sn, 1 As, 5 Sb and 4 Bi analogues taken from the literature. Evidence is provided for 1,5-chelation Sb · · · N via crystal structure determinations (5+1 (lit) Sb compounds) , 13C- and 29Si-NMR chemical shifts, 12;Sb and 12;I Mossbauer data (11 and 3 Sb compounds, respectively) , cyclic voltammetry (9 Sb compounds) and semi-empirical MO calculations on the Extended Huckel level …