Organozinnverbindungen XXXIII. Die erste Komplexbildung zwischen Organozinn- und Nitroderivaten: Reactionen der Zinn-Alkyl-Bindung

Article abstract of DOI:10.1016/0022-328X(89)85021-1

Although trimethylstannylbenzene in presence of MeCOCl*AlCl3 undergoes a carbodestannylation to give acetophenone, its 2-NO2, 3-NO2, 4-NO2, and 2,4-(NO2)2 derivatives (1a-d) exhibit a surprising, high activation of the aliphatic C-Sn bond (Me-Sn) which allows a single cleavage to give the corresponding dimethylchlorostannyl nitrobenzenes (2a-d) quantitatively without any aryl-Sn bond cleavage.A strong, hitherto unknown, intramolecular pentacoordination at the tin in 2a and 2d via complexation by the ortho nitro groups, is indicated by the IR, 1H, 13C, and 119Sn NMR spectral data.In contrast, reaction of iodine with 1a-d, or with 2a-d results in exclusive S_Ear ipso substitution of all stannyl groups.The mechanisms are discussed, preparative procedures and spectroscopic details are described.