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 pi-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 29Si and 73Ge nuclei. The small values of the hyperfine coupling constants a(29Si) and a(73Ge) clearly indicate the pi-character of both radicals, corresponding to a planar geometry and sp2 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.
Sekiguchi
Akira
A
Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571, Japan. sekiguch@staff.chem.tsukuba.ac.jp
Fukawa
Tomohide
T
Nakamoto
Masaaki
M
Lee
Vladimir Ya
VY
Ichinohe
Masaaki
M