Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane)
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- 作者：Eric M. Press ; Eric A. Marro ; Dr. Sravan K. Surampudi ; Dr. Maxime A. Siegler ; Dr. Joel A. Tang and Prof. Rebekka S. Klausen
- 刊名：Angewandte Chemie International Edition
- 出版年：2017
- 出版时间：January 9, 2017
- 年：2017
- 卷：56
- 期：2
- 页码：568-572
- 全文大小：1754K
- ISSN：1521-3773
文摘
We report a strategic synthesis of poly(cyclosilane), a well-defined polymer inspired by crystalline silicon. The synthetic strategy relies on the design of a functionalized cyclohexasilane monomer for transition-metal-promoted dehydrocoupling polymerization. Our approach takes advantage of the dual function of the phenylsilyl group, which serves a crucial role both in the synthesis of a novel α,ω-oligosilanyl dianion and as a latent electrophile. We show that the cyclohexasilane monomer prefers a chair conformation. The monomer design ensures enhanced reactivity in transition-metal-promoted dehydrocoupling polymerization relative to secondary silanes, such as methylphenylsilane. Comprehensive NMR spectroscopy yields a detailed picture of the polymer end-group structure and microstructure. Poly(cyclosilane) has red-shifted optical absorbance relative to the monomer. We synthesize a σ–π hybrid donor–acceptor polymer by catalytic hydrosilylation.