Highly stereoselective synthesis of arylene-silylene-vinylene polymers

Stereoregular trans-arylene-silylene-vinyl-ene polymers of M,,,=13100-34800 and PDI=1.62.9 of the general formulas CH2=CH-[-SiMe2C6H4SiMe2CH=CH-]-(16, 17, 18) and CH -CH-[-(R)CH=CHC6H,CH=CH-]- (where R=-Me2Si-P-C(6)H(4)SiMe2-, -Me-,Si-m-C6H4SiMe2- and -Me2SiC6H4-C6H4SiMe2-) (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) (PC gamma(3))(2)] (7). Such highly stereoregular products cannot be synthesized via ADMET polycondensation or ring opening metathesis ROM or polyaddition of hydridosilanes to acetylenes.