Studies on organosilicon reactive intermediates. VI. Photolysis of trisilanes containing heterocycles

✍ Scribed by Shi-Hui Wu; Hu Qian; Ge Wu; Nan Jiang

• Publisher: John Wiley and Sons
• Year: 1992
• Tongue: English
• Weight: 575 KB
• Volume: 3
• Category: Article
• ISSN: 1042-7163
• DOI: 10.1002/hc.520030522

✦ Synopsis

Both 2-phenyl-2-furylhexamethyltrisilane (1) and 2phenyl-2-thienylhexamethyltrisilane (2) were synthesized by conventional organometallic reactions. The photolysis of 1 in the presence of 2,3-dimethyl-1,3butadiene led to normal silylene-olefin addition and silylene C-H insertion reactions. However, when 2 was photolyzed in a methanol-cyclohexene system, an apparent radical reaction occurred. We suspect that the sulfur atom of the thienyl group strongly stabilizes a silyl radical. This result was supported by both identifying its typical radical reaction products and examining the ESR spectrum of its adduct with a radical trap.

INTR 0 D U CTI ON

Ever since Ishikawa and Kumada reported the generation of dimethylsilylene via photolysis of dodecamethylcyclohexasilane in 1970 [ 11, more and more silylenes have been generated by photolysis of polysilanes. This method has come to be recognized as a useful silylene source in silylene structure and reaction studies.

Although this method is widely used, relatively Dedicated to Prof. Yao-Zeng Huang on the occasion of his "To whom correspondence should be addressed.