Jg. Radziszewski et al., MULTIPLY-BONDED SILICON - MATRIX-ISOLATION AND CHEMICAL TRAPPING OF PRODUCTS OF PYROLYSIS AND PHOTOLYSIS OF TRIAZIDOPHENYLSILANE, Organometallics, 12(12), 1993, pp. 4816-4824
Triazidophenylsilane (1) yields phenyl isosilacyanide (3) upon irradia
tion in matrix isolation and by pyrolysis followed by trapping in nobl
e gas matrix. Annealing from 12 to 15 K causes significant changes in
the IR spectrum of photochemically produced 3, attributed to the relea
se of hydrostatic pressure in the matrix. The matrix reaction of pyrol
ytically produced 3 with t-BuOH to yield an independently synthesized
trapping adduct 4 has been followed spectrally. An aligned sample of 3
was produced by photoselection and polarized IR spectra were recorded
. The UV and IR absorption spectra of 3 have been interpreted and agre
e well with ab initio and semiempirical calculations. In contrast, the
intermediacy of benzenesilonitrile (2), a representative of a so far
unknown class of species with a -Si=N triple bond, in the photofragmen
tation of matrix-isolated 1, is merely strongly suggested but not prov
en by trapping of the photoproducts from matrix-isolated 1 with t-BuOH
to yield the adduct 5 in addition to 4. The silonitrile 2 did not acc
umulate in the matrix in amounts sufficient for spectral characterizat
ion.