Functionalization of Vinylspherosilicates by Ruthenium‐Catalyzed Silylative Coupling Reactions

Abstract

Highly effective functionalization of monovinylsiloxy heptaisobutylsilsesquioxane and octavinylspherosilicate of the formula (ViMe 2 SiO)(iBu) 7 Si 8 O 12 (1) and (ViMe 2 SiO) 8 Si 8 O 12 (2), respectively, with a variety of olefins, by using a Ru(H)(Cl)-(CO)(PCy 3 ) 2 -catalyzed silylative coupling procedure is reported. The cross-metathesis reaction catalyzed by a ruthenium-carbene complex does not proceed for this system. Whereas the reaction of 1 and 2 with styrene takes place

Highly effective synthesis of vinylfunctionalised cubic silsesquioxanes

“…With the use of silylative coupling and cross-metathesis, we reported the highly-effective functionalisation of octavinylsilsesquioxanes Vi 8 T 8 with a variety of olefins [6]. Moreover, we have demonstrated the high activity of ruthenium hydride complexes in the silylative coupling of vinylsubstituted spherosilicates [7] with styrene and some other olefins.…”

Epoxy Elastomers Modified with Silsesquioxane

“…Such a relationship seems to indicate either the presence of plasticizing effect of POSS-OG in Ether1,4/ POSS-OG/D2000 and Ether1,6/POSS-OG/ D2000 compositions, or reduction in crosslinking density due to extensive cyclization caused by POSS-OG aggregation. One should bear in mind that POSS-OG used by us is in fact a spherosilicate [25] with extra eight -OSi(CH 3 ) 2 groups between the silsesquioxane cage and propylglycidyl groups that may be responsible for the plasticizing effect. In our opinion, the fact that the reduced modulus was observed by adding 10% of the modifier may have been caused by the increased inhomogeneity of the emerging networks.…”

Efficient Functionalisation of Cubic Monovinylsilsesquioxanes via Cross‐Metathesis and Silylative Coupling with Olefins in the Presence of Ruthenium Complexes

“…[11] A highly efficient cross-metathesis of octavinylsilsesquioxanes with selected olefins in the presence of Grubbs catalyst (1) has also been realised in our laboratory. [12] Moreover, we have demonstrated the high activity of ruthenium hydride complexes in the silylative coupling of vinyl-substituted silsesquioxanes [12] and spherosilicates [13] with styrene and some other olefins.…”