0000000000820380
AUTHOR
Norbert Kleiner
Über polyplumbane
Abstract Diplumbanes Pb 2 R 3 R′ 3 (R,R′ = Ph, o -Tol, p -Tol) have been synthesized from R 3 PbLi and R′ 3 PbCl at −60°C in THF. Mass, 13 C and 207 Pb NMR spectra of the products exhibit migrations of R, R′ in the transition state (R 3 PbLi + ClPbR′ 3 ) leading to a complex distribution of the substituents (δ( 207 Pb) with respect to PbMe 4 −70 to −95 ppm). The PbPb stretching vibration (100 to 115 cm −1 ) couples with a lattice vibration giving rise to a single intensive Raman line. The crystal structure of Pb 2 Ph 3 ( p -Tol) 3 has been determined and refined to R = 0.155. Two independent molecules are disordered and have identical distribution of the substituents Ph( p -Tol) 2 PbPbPh …
Über gemischte bindungen in der IV. Hauptgruppe
Abstract The reaction of Ph 3 PbLi with Ph 3 SnCl or Ph 3 GeCl gives Ph 3 PbSnPh 3 and Ph 2 PbGePh 3 , respectively; there is no reaction with Ph 3 SiCl. Ph 3 SiLi reacts with Ph 3 PbCl to form a regular 1 : 1 Pb 2 Ph 6 · Si 2 Ph 6 phase. The compounds have been investigated by mass, NMR and vibrational spectra: 207 Pb NMR chemical shifts with respect to PbMe 2 −79.8 (Pb 2 Ph 6 ), −256.5 (Ph 3 PbSnPh 3 ), −271.5 ppm (Ph 3 PbGePh 3 ); stretching vibrations 112 (PbPb), 125 (PbSn), 138 cm −1 (PbGe). The crystal structures have been determined and refined to R = 0.061 (Ph 3 PbSnPh 3 , −40°C), 0.053 (Ph 3 PbGePh 3 , −50°C), 0.068 (Pb 2 Ph 6 · Si 2 Ph 6 , 20°C); bond lengths 285 (PbPb),…