Journal of the American Chemical Society, Vol.124, No.33, 9865-9869, 2002
Isolable silyl and germyl radicals lacking conjugation with pi-bonds: Synthesis, characterization, and reactivity
The one-electron oxidation reaction of tris[di-tert-butyl(methyl)silyl]silyl and -germyl anions with dichlorogermylene-dioxane complex results in the formation of stable tris[di-tert-butyl(methyl)silyl]silyl and -germyl radicals 1 and 2, representing the first isolable radical species of heavier Group 14 elements lacking stabilization by conjugation with A-bonds. The crystal structures of both silyl and germyl radicals 1 and 2 showed a completely planar geometry around the radical centers. The ESR spectra of 1 and 2 showed strong signals with characteristic satellites due to the coupling with the Si-29 and Ge-73 nuclei. The small values of the hyperfine coupling constants a(Si-29) and a(Ge-73) clearly indicate the A-character of both radicals, corresponding to a planar geometry and sp(2) hybridization of the radical centers. Both 1 and 2 easily undergo halogenation reactions with carbon tetrachloride, 1,2-dibromoethane, and benzyl bromide to form the corresponding halosilanes and halogermanes.