994-30-9Relevant articles and documents
CO2 laser excitation of triethylsilane: Time resolved luminescence of diethylsilyl radical
Papagiannakopoulos,Lazarou
, p. 857 - 867 (1994)
The infrared multiphoton excitation of triethylsilane in the gas phase, with a pulsed CO2 laser at high intensities (I>700 MW/cm2), produced an intense luminescence. The spectrum and time profile of this luminescence was studied as a function of pressure, and laser frequency. The radiative lifetime of this emission was 357±10 ns, and the quenching rates by Cl2 and NO were determined from lifetime measurements. A reasonable mechanism for the interpretation of this luminescence involves the initial infrared multiphoton decomposition of triethylsilane, followed by the secondary infrared multiphoton excitation of the primary photofragment diethylsilyl radical, which subsequently undergoes relaxation to an excited electronic state. The addition of O2 resulted in a new chemiluminescence at shorter wavelengths, which corresponds to the SiO* chromophore group.
Oxidation of Triorganosilanes and Related Compounds by Chlorine Dioxide
Grabovskiy,Kabal’nova
, p. 2391 - 2402 (2022/01/22)
Abstract: Oxidation of triethylsilane, tert-butyldimethylsilane, dimethylphenylsilane, triphenylsilane, 1,1,1,2tetramethyl-2-phenyldisilane, tris(trimethylsilyl)silane, hexamethyldisilane, tetrakis(trimethylsilyl)silane, 1,1,3,3tetraisopropyldisiloxane with chlorine dioxide was carried out. The reaction products of studied triorganosilanes with chlorine dioxide in an acetonitrile solution were the corresponding silanols and siloxanes. A mechanism explaining the formation of products and the observed regularities of the oxidation of silanes with chlorine dioxide has been proposed. A thermochemical analysis of some possible pathways in the gas phase using methods G4, G3, M05, and in an acetonitrile solution by the SMD-M05 method was carried out. The oxidation process can occur both with the participation of ionic and radical intermediates, depending on the structure of the oxidized substrate and medium.
Rh(iii)-Catalysed solvent-free hydrodehalogenation of alkyl halides by tertiary silanes
Almenara,Azpeitia,Garralda,Huertos
supporting information, p. 16225 - 16231 (2018/11/30)
Efficient catalytic reduction of CDCl3 and other alkyl halides, including persistent organic pollutants, by different tertiary silanes using the unsaturated silyl-hydrido-Rh(iii) complex {Rh(H)[SiMe2(o-C6H4SMe)](PPh3)2}[BArF4] as a pre-catalyst is accomplished. The reactions are performed in a solvent-free manner. On account of experimental evidence, a simplified catalytic cycle is suggested for the hydrodehalogenation of CDCl3.
B(C6F5)3-Catalyzed Selective Chlorination of Hydrosilanes
Chulsky, Karina,Dobrovetsky, Roman
supporting information, p. 4744 - 4748 (2017/04/11)
The chlorination of Si?H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl2, and CCl4. The catalytic chlorination of silanes often involves the use of expensive transition-metal catalysts. By a new simple, selective, and highly efficient catalytic metal-free method for the chlorination of Si?H bonds, mono-, di-, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O?B(C6F5)3 and HCl with the release of H2 as a by-product. The hydrides in di- and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O?B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.