813-43-4Relevant academic research and scientific papers
Electrochemical synthesis of symmetrical difunctional disilanes as precursors for organofunctional silanes
Grogger, Christa,Loidl, Bernhard,Stueger, Harald,Kammel, Thomas,Pachaly, Bernd
, p. 105 - 110 (2007/10/03)
Difunctional disilanes of the general type XR2SiSiR2X (1-5) (X = OMe, H; R = Me, Ph, H) have been synthesized by electrolysis of the appropriate chlorosilanes XR2SiCl in an undivided cell with a constant current supply and in the absence of any complexing agent. Reduction potentials of the chlorosilane starting materials derived from cyclic voltammetry measurements were used to rationalize the results of preparative electrolyses. Organofunctional silanes of the general formula MeO(Me 2)SiC6H4Y (6a-c, 7) were subsequently obtained by the reaction of sym-dimethoxytetramethyldisilane (1) with NaOMe in the presence of p-functional aryl bromides BrC6H4Y (Y = OMe, NEt2, NH2).
Mercury-sensitized photolysis of Me2SiH2 the disproportionation reactions of the Me2SiH radical
Kerst,Potzinger
, p. 1071 - 1078 (2007/10/03)
Mercury-sensitized photolysis of Me2SiH2 yields in the primary step an Me2HSi radical and an H atom with a quantum yield of one. The Me2HSi radicals undergo a combination reaction [k(2)] as well as two kinds of disproportionate reactions leading to dimethylsilylene [k(3)] and 1-methylsilaethene [k(4)]. The following branching ratios have been determined: k(3)/[k(2) + k(3) + k(4)] = 0.64 ± 0.10 and k(4)/[k(2) + k(3) + k(4)] ≥ 0.007. For Me3Si radicals the branching ratio for disproportionation was also determined and a value of 0.063 was obtained.
GAS-PHASE PHOTOCHEMICAL REACTIONS OF DODECAMETHYLCYCLOHEXASILANE WITH SILICON COMPOUNDS. KINETICS OF SOME INSERTION REACTIONS OF DIMETHYLSILYLENE
Davidson, Iain M.T.,Ostah, Naaman A.
, p. 149 - 158 (2007/10/02)
Attempts to measure the kinetics of gas-phase insertion reactions of dimethylsilylene, generated by photolysis of dodecamethylcyclohexasilane, are described.Insertion of dimethylsilylene into silicon-hydrogen bonds was the main reaction with trimethylsilane, pentamethyldisilane, and sym-tetramethyldisilane; in all cases the activation energy for insertion was zero, and the rate constants were in the ratio of 1:3.1:4.3.Dimethylsilylene also inserted cleanly into hydrogen chloride with an activation energy of 28 kJ mol-1.Photochemical reactions with methylchlorosilanes were much more complex, involving little or no silylene chemistry; such reactions as did occur appeared to proceed almost entirely by radical mechanisms.
