Synthesis, Properties, Oxidation, and Electrochemistry of 1,2-Dichalcogenins
| Autor: | George S. Wilson,§ and, Jürgen Fabian, Chunhong He, Marc Birringer, Mohan Thiruvazhi, Quangsheng Qian, Richard S. Glass, Chuangxing Guo, Xing Zhang, Edward Lorance, T. Benjamin Schroeder, Eric Block, Zhixing Shan, Russell Deorazio |
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| Rok vydání: | 2000 |
| Předmět: | |
| Zdroj: | Journal of the American Chemical Society. 122:5052-5064 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | Syntheses are presented of the 1,2-dichalcogenins: 1,2-dithiin, 1,2-diselenin, and 2-selenathiin, both substituted and unsubstituted. 1,2-Dithiin and 1,2-diselenin are prepared by reaction of PhCH2XNa (X = S or Se) with 1,4-bis(trimethylsilyl)-1,3-butadiyne followed by reductive cleavage and oxidation. 2-Selenathiin is similarly prepared using a mixture of PhCH2SeNa and PhCH2SNa. Reaction of titanacyclopentadienes with (SCN)2 or (SeCN)2 followed by bis(thiocyanate) or bis(selenocyanate) cyclization affords substituted 1,2-dithiins or 1,2-diselenins, respectively. With S2Cl2, 1,2-dithiins are directly formed from titanacyclopentadienes. Oxidation of 1,2-dithiins and 1,2-diselenins gives the corresponding 1-oxide and, with 1,2-dithiins and excess oxidant, 1,1-dioxides; oxidation of 2-selenathiin gives the 2-oxide. Electrochemical oxidation of 1,2-dichalcogenins, which have a twisted geometry, affords planar radical cations by an EC mechanism. One-electron AlCl3 oxidation of 3,6-diphenyl-1,2-dithiin gives t... |
| Databáze: | OpenAIRE |
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