کد مقاله | کد نشریه | سال انتشار | مقاله انگلیسی | نسخه تمام متن |
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1325261 | 1499945 | 2009 | 8 صفحه PDF | دانلود رایگان |
![عکس صفحه اول مقاله: Synthesis of silicon-functionalized 7-silanorbornadienes and their thermolysis and photolysis Synthesis of silicon-functionalized 7-silanorbornadienes and their thermolysis and photolysis](/preview/png/1325261.png)
A series of 7-silanorbornadienes were prepared and characterized by X-ray crystallographic analysis. 2,3-Benzo-7-mesityl-1,4,5,6-tetraphenyl-7-silanorbornadiene (1a) was prepared by the [4+2] cycloaddition reaction of 1-mesityl-2,3,4,5-tetraphenyl-1-sila-2,4-cyclopentadiene (4) with benzyne. 7-Hydro 1a was converted into 7-chloro-substituted silanorbornadiene 1b. Treatment of 1b with lithium phenylamide and lithium phenylthiolate gave 7-phenylamino-substituted silanorbornadiene 1c and 7-phenylthio-substituted silanorbornadiene 1d, respectively. Reductive lithiation of 1b with lithium naphthalenide afforded 7-lithiated silanorbornadiene 1f, which reacted with chlorotrimethylsilane to give 7-trimethylsilyl-substituted silanorbornadiene 1e. Stereochemistry at the bridging silicon during these transformations was determined by X-ray crystallographic analysis. Thermolysis of 1 produced corresponding silylenes 5, which were trapped with triethylsilane to give disilanes 6. Photolysis of 1 except 1c also afforded corresponding silylenes 5. Theoretical calculation of the models of silanorbornadienes was performed at the MP2/6-31+G(d, p) level.
Silicon-functionalized 7-silanorbornadienes were prepared and underwent thermolysis and photolysis, giving the corresponding silylenes.Figure optionsDownload as PowerPoint slide
Journal: Journal of Organometallic Chemistry - Volume 694, Issues 9–10, 15 April 2009, Pages 1419–1426