80785-72-4Relevant articles and documents
Emission from the Excited State of Tetraneopentyldisilene
Shizuka, Haruo,Tanaka, Hideaki,Okazaki, Katsuhiko,Kato, Motohiko,Watanabe, Hamao,et al.
, p. 748 - 750 (1986)
Fluorescence from tetraneopentyldisilene containing only a silicon-silicon double bond as chromophore is observed with a large Stokes shift (7300 cm-1) in methylcyclohexane-isopentane glass at 77 K.
Matrix Effect. Dimerization of Silylenes at 77 K in the Matrix
Sekiguchi, Akira,Hagiwara, Kazuyoshi,Ando, Wataru
, p. 209 - 210 (1987)
The dimerization of silylenes was studied in hydrocarbon matrix ranging in viscosity from 1E6 to 1E12 at 77 K.The silylenes dimerized to disilenes in soft matrix at 77 K without annealing.
Reactivity of sulfonyl-containing compounds with ditetrelenes
Tashkandi, Nada Y.,Bourque, Jeremy L.,Baines, Kim M.
, p. 15451 - 15457 (2017/11/21)
The addition of a variety of sulfones and a sulfoxide to ditetrelenes (a disilene and a digermene) was examined. The reaction of benzenesulfonyl chloride with tetramesityldisilene or tetramesityldigermene results in the formation of the 1,2-addition products, 2-chlorotetramesityldisilyl- or digermylbenzenesulfinate. The addition of p-toluenesulfonyl chloride to the disilene gave the analogous product, 2-chlorotetramesityldisilyl p-toluenesulfinate. In contrast, benzenesulfonyl fluoride, diphenyl and dimethyl sulfone did not react with either the disilene or the digermene. The unprecedented formation of the sulfinates reveals a selective 2-electron reduction of the sulfur centres using ditetrelenes. The addition reactions of sulfonyl compounds illustrates the potential of ditetrelenes to serve as reducing agents which react rapidly, at room temperature under mild conditions. The reaction of tetramesityldisilene with diphenyl sulfoxide resulted in the formation of tetramesityloxadisilirane and with benzene sulfonic acid resulted in the formation of 1,1,2,2-tetramesityldisilyl benzenesulfonate.
Fast kinetics study of the reactions of transient silylenes with alcohols. Direct detection of silylene-alcohol complexes in solution
Leigh, William J.,Kostina, Svetlana S.,Bhattacharya, Adroha,Moiseev, Andrey G.
body text, p. 662 - 670 (2010/05/15)
The kinetic behavior of dimethyl-, diphenyl-, and dimesitylsilylene in hexanes solution in the presence of methanol (MeOH), tert-butanol (t-BuOH), and the respective O-deuterated isotopomers has been studied, with the goal of elucidating a detailed mechanism for the formal O-H insertion reaction of transient silylenes with alcohols in solution. The data are in all cases consistent with a mechanism involving the intermediacy of the corresponding silylene-alcohol Lewis acid-base complexes, which have been detected directly for each of the SiMe2-ROL and SiPh2-ROL (L = H or D) systems that were studied. Complexation proceeds effectively irreversibly (Keq ≥ 2 x 105 M-1) and at close to the diffusion-controlled rate in these cases. In contrast, the kinetic and spectroscopic behavior observed for SiMeS2 in the presence of these alcohols indicates the SiMeS2-ROL complexes are involved as steady-state intermediates, formed reversibly and 10-100 times more slowly than is the case with SiMe2 and SiPh2. Product formation from the silylene-alcohol complexes is shown to proceed via catalytic proton transfer by a second molecule of alcohol, the rate of which exceeds that of unimolecular intracomplex H-migration in all cases, even at submillimolar alcohol concentrations. The catalytic rate constants range from 109 to 1010 M-1 s-1 for the SiMe2-ROH and SiPh2-ROH complexes, sufficiently fast that the isotope effect ranges from ca. 2.5 to close to unity for all but the SiPh2-t-BuOL complex, where it is remarkably large (kHH/kDD = 10.8 ± 2.4). The value is consistent with a mechanism for catalysis involving double proton transfer within a cyclic five-membered transition state. The isotope effects on the ratio of the rate constants for catalytic proton transfer and dissociation of the SiMeS2-MeOH and SiMeS2-t-BuOH complexes suggest that a different mechanism for catalytic proton transfer is involved in the case of the sterically hindered diarylsilylene.
