کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1325908 | 977409 | 2008 | 9 صفحه PDF | دانلود رایگان |
The reaction pathway for the formation of the trimethylsiloxysilyllithium compounds (Me3SiO)RR′SiLi (2a: R = Et, 2b: R = iPr, 2c: R = 2,4,6-Me3C6H2 (Mes); 2a–c: R′ = Ph; 2d: R = R′ = Mes) starting from the conversion of the corresponding trimethylsiloxychlorosilanes (Me3SiO)RR′SiCl (1a–d) in the presence of excess lithium in a mixture of THF/diethyl ether/n-pentane at −110 °C was investigated.The trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (1a: R = Et, 1b: R = iPr, 1c: R = Mes) react with lithium to give initially the trimethylsiloxysilyllithium compounds (Me3SiO)RPhSiLi (2a–c). These siloxysilyllithiums 2 couple partially with more trimethylsiloxychlorosilanes 1 to produce the siloxydisilanes (Me3SiO)RPhSi–SiPhR(OSiMe3) (Ia–c), and they undergo bimolecular self-condensation affording the trimethylsiloxydisilanyllithium compounds (Me3SiO)RPhSi–RPhSiLi (3a–c). The siloxydisilanes I are cleaved by excess of lithium to give the trimethylsiloxysilyllithiums (Me3SiO)RPhSiLi (2). In the case of the two trimethylsiloxydisilanyllithiums (Me3SiO)RPhSi–RPhSiLi (3a: R = Et, 3b: R = iPr) a reaction with more trimethylsiloxychlorosilanes (Me3SiO)RPhSiCl (1a, 1b) takes place under formation of siloxytrisilanes (Me3SiO)RPhSi–RPhSi–SiPhR(OSiMe3) (IIa: R = Et, IIb: R = iPr) which are cleaved by lithium to yield the trimethylsiloxysilyllithiums (Me3SiO)RPhSiLi (2a, 2b) and the trimethylsiloxydisilanyllithiums (Me3SiO)RPhSi–RPhSiLi (3a, 3b). The dimesityl-trimethylsiloxy-silyllithium (Me3SiO)Mes2SiLi (2d) was obtained directly by reaction of the trimethylsiloxychlorosilane (Me3SiO)Mes2SiCl (1d) and lithium without formation of the siloxydisilane intermediate. Both silyllithium compounds 2 and 3 were trapped with HMe2SiCl giving the products (Me3SiO)RR′Si–SiMe2H and (Me3SiO)RPhSi–RPhSi–SiMe2H.
Depending on substituents the reaction pathways of the formation of (Me3SiO)RR′SiLi differ. The formation of (Me3SiO)RPhSiLi (R = Et, iPr) takes place via the intermediates (Me3SiO)RPhSi–(RPhSi)n–SiPhR(OSiMe3) (n = 0, 1) which are cleaved by excess lithium. (Me3SiO)MesPhSiLi is formed via Me3SiO(MesPhSi)2OSiMe3 and its following cleavage by Li. (Me3SiO)Mes2SiLi is directly obtained by reductive lithiation without formation of intermediates.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 693, Issue 7, 1 April 2008, Pages 1283–1291