Highly Stereoselective Synthesis of Arylene‐Silylene‐Vinylene Polymers

Abstract

Dedicated to Professor Julian Chojnowski on the occasion of his 70 th birthday in recognition of his significant contribution to organosilicon polymer chemistry.Abstract: Stereoregular trans-arylene-silylene-vinylene polymers of M w ¼ 13100 -34800 and PDI ¼ 1.6 -2.9 of the general formulasSiMe 2 À and À Me 2 SiC 6 H 4 -C 6 H 4 SiMe 2 À ) (19, 20, 21) have been effectively synthesized via silylative coupling (SC) homopolycondensation of bis(vinyldimethylsilyl)arenes (10, 12, 14) and cross-polycondensation of 4-(vinyldimethylsilyl)styrene (11) as well as cross-copolycondensation of bis(vinyldimethylsilyl)arenes (10, 12 and 14) with 1,4-divinylbenzene (9) catalyzed by [RuH(Cl)(CO) (PCy 3 ) 2 ] (7). Such highly stereoregular products cannot be synthesized via ADMET polycondensation or ring opening metathesis ROM or polyaddition of hydridosilanes to acetylenes.

Silylative coupling of olefins with vinylsilanes in the synthesis of functionalized alkenes

“…Reactivities of divinylsubstituted organosilicon compounds in the competitive processes of catalytic polycondensation [26][27][28][29] and intramolecular cyclization [30][31][32][33][34] by silylative coupling in the presence of ruthenium(II) or rhodium(I) complexes have also been studied. He was a postdoctoral fellow with Professor Andre Mortreux at the Lille University (France).…”

(E)-1,2-Bis{4-[dimethyl(vinyl)silyl]phenyl}ethene

“…For related literature, see: JanBen & Krause (2005); Maciejewski et al (2003); Majchrzak et al (2005Majchrzak et al ( , 2007.…”

“…During first step, the well know metathesis reaction of 4-bromostyrene was applied to obtain {(E)-1,2-bis(4-bromophenyl)}ethene which was used as a substrate for the second step, the typical reaction between an aryl-halide derivative of an olefin, a Grignard reagent generated in situ and vinylchlorosilane. This kind of vinylsilane-stilbene can be used as a very efficient monomer for the synthesis of arylene-silylene-vinylene polymers, polycarbosilanes or co-polymers with suitable aromatic olefin via silylative coupling polycondensation (SCP) or polyhydrosilylation reactions (Majchrzak et al, 2005(Majchrzak et al, , 2007Maciejewski et al, 2003).…”

(E)-1,2-Bis(diphenylmethylsilyl)ethene

“…ruthenium, rhodium); in which the the M-H and M-Si bonds were either initially introduced or generated in the solution (Marciniec, 2005;Marciniec & Pietraszuk, 2003). Under optimal conditions (catalyst: [RuCl 2 (CO) 3 ] 2 or [RuHCl(CO)(PCy 3 ) 2 ]), this process has become an excellent method for the selective synthesis of (E)-1,2-bis(silyl)ethenes (Majchrzak et al, 2005;Marciniec & Lewandowski, 1997), and macromolecular organosilicon compounds containing (E)-1,2-bis(silyl) fragments (Marciniec & Małecka, 1999;Majchrzak et al, 2000;. The number of reported structures of 1,2-unsubstituted and substituted bis(silyl)ethene is limited and most of them possess trans configurations.…”