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- W1978892110 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 and 207Pb NMR data. This nucleophilic attack originates from the π-basicity and the charge flow from the ligands into a σ∗-LUMO at Ge, Sn or Pb. The electronegativity of the ligands at Ge, Sn or Pb inhibits nucleophilic attack. The ligand sequences PhCl2Ph2Cl>PhCl>Ph3 and Ph2IPh2BrPh2OPhPh2ClPh2F hold for an increasing approach N…Ge/Sn/Pb). The δ values (13C) of the α-methylene in CDCl3 solution are shifted distinctly to high frequency by increasing the approach between the Me2N donor and the central atom. A qualitative discussion of 119Sn NMR chemical shifts and spin-spin coupling constants is given, which supports the arguments on the basis of interactions of frontier orbitals." @default.
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- W1978892110 date "1998-07-01" @default.
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- W1978892110 title "Nucleophilic attack within Ge, Sn and Pb complexes containing Me2N(CH2)3—as a potential intramolecular donor ligand" @default.
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- W1978892110 doi "https://doi.org/10.1016/s0020-1693(98)00071-1" @default.
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