Highly stereoselective synthesis of novel trans-thiophenylene-silylene-vinylene-arylene molecular and macromolecular compounds

Novel stereoregular molecular compounds 8–13 containing thiophenylene-silylene-vinylene-phenylene units have been synthesised via highly effective silylative coupling of styrene and 1,4-divinylbenzene (7) with respective vinylsilylthiophenes (3, 4) and bis(vinylsilyl)thiophenes (5, 6) catalyzed by RuHClCO(PCy3)2. Respective copolymers (14, 15) were produced via silylative copolycondensation of 5 and 6 with 7. All products were isolated and characterised by NMR, MS, HRMS and two of them 10 and 11 by X-ray method. Catalytic study as well as stoichiometric reactions of Ru–H (1) with 2-(vinylsilyl)thiophene (3) and Ru–Si (16) with styrene confirmed the mechanism of the silylative coupling olefins with vinylsilicon compounds.

Graphical abstractNovel stereoregular trans-thiophenylene-silylene-vinylene-arylene molecular and polymeric material derivatives have been easily synthesized via silylative coupling (SC) reaction catalysed by ruthenium-hydride complex.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Vinylsilylthiophenes can be easily functionalisation to π-conjugated organosilicon materials. ► Silylative coupling permits modification of multivinylsilylthionyl derivatives. ► Trans-thiophenylene-silylene-vinylene-arylene compounds are attractive, potential materials for optoelectronic devices.