63562-64-1Relevant academic research and scientific papers
Reactive intermediates from the photolysis of methylpentaphenyl- and pentamethylphenyldisilane
Sluggett, Gregory W.,Leigh, William J.
, p. 1195 - 1201 (1992)
The photochemistry of methylpentaphenyldisilane (1) and pentamethylphenyldisilane (7) has been investigated using nanosecond laser flash photolysis techniques. Flash photolysis of 1 with 248-nm light in acetonitrile or isooctane solution gives rise to a complex mixture of transient species. A strongly-absorbing transient with λmax, = 490 nm and τ ≤ 1.7 μs (in acetonitrile) has been assigned a 1,3,5-(1-sila)triene structure on the basis of comparisons to the transient spectroscopic behavior of 7, which is known to rearrange to a silatriene intermediate in high yield upon photolysis, and on the basis of comparisons of the reactivity of these species toward water, a series of alcohols, acetone, acetic acid, ethyl acetate, oxygen, alkenes, and silanes. The extinction coefficient for the long-wavelength absorption band of the silatriene from 1 has been estimated. Silyl-centered radicals have also been identified in the transient mixture on the basis of their UV spectra and quenching with 2-bromopropane. Quenching of the silatrienes from 1 and 7 is linear in concentration for oxygen, acetone, cyclohexene, and 2,3-dimethylbutadiene. While quenching of the two silatrienes by 2,2,2-trifluoroethanol and acetic acid are also linear in concentration, water, methanol, ethanol, and tert-butyl alcohol give rise to curved quenching plots. These results are consistent with an addition mechanism which involves initial, reversible formation of a zwitterionic silene-alcohol complex, followed by competing ultra- and intermolecular proton transfer. Rate constants for the bi- and termolecular quenching processes have been determined by quadratic least-squares analysis of the quenching plots. A deuterium isotope effect of kH/kD ≈ 1.7 has been measured for the intracomplex proton-transfer process for the reaction of the two silatrienes with water. Similar, nonlinear behavior is observed for the quenching of the silatrienes by methoxytrimethylsilane.
ORTHO LITHIATION DIRECTED BY AMINO GROUPS ON SILICON IN PHENYLSILANE DERIVATIVES
Tamao, Kohei,Yao, Hajime,Tsutsumi, Yasushi,Abe, Hideyuki,Hayashi, Takashi,Ito, Yoshihiko
, p. 2925 - 2928 (2007/10/02)
Phenylsilanes, which contain trimethylethylenediamino (Me2NCH2CH2NMe-) group(s) on silicon, undergo selective ortho lithiation by treatment with t-BuLi, providing a new method for the synthesis of ortho substituted phenylsilane derivatives.
