Synthesis, structure, and spatial arrangement of Si-substituted N-(dimethylsilylmethyl)imides

The synthesis of N-(chlorodimethylsilylmethyl)succinimide and N-(chlorodimethylsilylmethyl)-glutarimide by the reaction of the corresponding N-trimethylsilylimides with chlorodimethylsilane and by the reaction of unsubstituted imides with a mixture of hexamethyldisilazane with dimethylchloromethylchlorosilane is described. The formation of N-(chlorodimethylsilylmethyl)succinimide is followed by substitution by the silicon atom, which, depending on the reagent ratio, provides N-(dimethylsuccinimidomethyl)succinimide as the major or minor product. ¹H, ¹³C, and ²⁹Si NMR spectroscopy and X-ray diffraction analysis showed that the silicon atom in N-(chlorodimethylsilylmethyl)glutarimide is five-coordinate. By contrast, in N-(chlorodimethylsilylmethyl)succinimide and N-(dimethylsuccinimidomethyl)succinimide, according to NMR and X-ray diffraction data, the silicon atom is four-coordinate. Quantumchemical calculations by the AM1 method show that the molecular conformations of N-(chlorodimethylsilylmethyl)imides containing an intramolecular OSi bond are not energetically most favorable in the gas phase.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 10, 2004, pp. 1617–1623.Original Russian Text Copyright © 2004 by Pogozhikh, Ovchinnikov, Kramarova, Negrebetskii, Shipov, Albanov, Voronkov, Pestunovich, Baukov.This revised version was published online in April 2005 with a corrected cover date.