Premium
Synthesis of a Fragment of Crystalline Silicon: Poly(Cyclosilane)
Author(s) -
Press Eric M.,
Marro Eric A.,
Surampudi Sravan K.,
Siegler Maxime A.,
Tang Joel A.,
Klausen Rebekka S.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201610208
Subject(s) - monomer , hydrosilylation , polymerization , polymer chemistry , polymer , materials science , silanes , reactivity (psychology) , ring opening polymerization , chemistry , photochemistry , catalysis , silane , organic chemistry , medicine , alternative medicine , pathology
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.