Metal-free polymerization of phenylsilane: tris(pentafluorophenyl)borane-catalyzed synthesis of branched polysilanes at elevated temperatures.
The strong organoborane Lewis acid B(C6F5)3 catalyzes the polymerization of phenylsilane at elevated temperatures forming benzene and SiH4 as side-products. The resulting polymer is a branched polysilane with an irregular substitution pattern, as revealed by 2D NMR spectroscopy. Having explored the mechanism of this novel metal-free polymerization by computational chemistry methods at the DFT level, we have suggested that unusual cationic active species, namely monomer-stabilized silyl cations, propagate the polymerization. Hydride abstraction of SiH3 moiety by the catalyst in the initiation step was found to be kinetically preferred by around 9 kcal mol(-1) over activation by coordination …
The Next 100 Years of Polymer Science
International audience; The year 2020 marks the 100th anniversary of the first article on poly merization, published by Hermann Staudinger. It is Staudinger who realized that polymers consist of long chains of covalently linked building blocks. Polymers have had a tremendous impact on the society ever since this initial publication. People live in a world that is almost impossible to imagine without synthetic polymers. But what does the future hold for polymer science? In this article, the editors and advisory board of Macromolecular Chemistry and Physics reflect on this question.