4095-10-7Relevant articles and documents
Laser Pulse Photolysis of 7-Silanorbornadiene in Solution: Experimental and AM1 Studies of Complexation between Silylenes and CHBr3
Taraban, Marc B.,Plyusnin, Victor F.,Volkova, Olga S.,Grivin, Vyacheslav P.,Leshina, Tatyana V.,et al.
, p. 14719 - 14725 (1995)
The quantum yield (0.95 +/- 0.1) for the decomposition of 7,7-dimethyl-1,4,5,6-tetraphenyl-2,3-benzo-7-silanorbornadiene (Ib) in hexane at room temperature has been determined by the laser pulse photolysis technique.Reaction rate constants of the generated dimethylsilylene with bromoform (4.4 * 107 M-1 s-1) and Ib (5.7 * 109 M-1 s-1) have been measured.It is suggested that the reaction of Me2Si: with CHBr3 occurs via the formation of an intermediate complex (λmax = 338 nm, ε =1280 M-1 cm-1).The bimolecular rate constant for decay of the complex (2k = 1.61 * 109 M-1 s-1) has also been estimated.Semi-empirical PM3 calculations of the model reaction between the singlet SiH2 and CHBr3 show the formation at the first step of the reaction of a donor-acceptor complex stabilized by interactions between a vacant p-AO of SiH2 and a lone pair of one of the Br atoms.Such a complex should be rather stable both toward dissociation into the starting reagents (E = 23.3 kcal/mol) and further rearrangement into the insertion product, Br(H2)SiCHBr2 (E = 22.3 kcal/mol).
Reactions of methyl(pentafluorophenyl)- and methyl(pentafluorophenyl)phenylsilanes with electrophiles. A convenient preparative route to halogeno(methyl)pentafluorophenylsilanes C6F5SiMe2X and C6F5SiMeX2 (X=F, Cl and Br)
Frohn,Lewin,Bardin
, p. 255 - 263 (2007/10/03)
Halogeno(methyl)pentafluorophenylsilanes C6F5SiMenX3-n (n=1, 2) (X=F, Cl, Br) were prepared in good yields from the corresponding phenylsilanes C6F5SiMenPh3-n by reactions with the electrophiles aHF, HCl-AlCl3, Br2-AlBr3 or AlX3 (X=Cl, Br) halogenated hydrocarbons. Additionally, reactions of C6F5SiMe3 and (C6F5)2SiMe2 with selected electrophiles were studied.
