Olefin Metathesis of Vinylgermanium Derivatives as Method for the Synthesis of Functionalized Cubic and Double‐Decker Germasilsesquioxanes

Abstract

Fort he first time,o lefin cross metathesis has been developed for vinylgermanium compounds. This paper also marks the first case of transition metal-catalyzed functionalization of heterosilsesquioxanes,w hich in our case are cubic vinylgermasilsesquioxanes and newly synthesizedd i(vinylgermyl)substituted double-decker silsesquioxane.T hese processes leadt oaseries of new molecular, unsaturated mono-a nd divinyl-substituted germasilsesquioxanes, which can be potentially applied as precursors for optoelectronics and for the synthesis of new advanced materials.A dditionally,p reliminary tests of metathetic copolymerization of divinylsubstituted double-deckerd igermasilsesquioxanes (DDSQ-2ViGe) with selected diolefins provedt ob ev ery promising and resulted in the synthesis of novels tereoregular trans-germasilsesquioxyl-vinylene-phenylene macromolecular derivatives.A ll newly obtained compounds were isolated andc haracterized by mass and spectroscopic methods.Scheme5.Cross-metathesis of DDSQ-2ViGe with olefins.

Highly Efficient Route for the Synthesis of a Novel Generation of Tetraorganofunctional Double‐decker Type of Silsesquioxanes

“…At the same time, chemists are looking for synthetic routes exploiting among others hydrosilylation reaction to obtain novel, functionalized Si-based reagents with a specific structure such as silsesquioxanes. [17][18][19][20][21][22][23][24][25][26][27] While hydrosilylation of olefins with silanes has been widely studied, [3,28] the reports on T 8 silsesquioxanes are limited [5,6,[29][30][31][32][33][34] and for double-decker systems of both closed (D 2 T 8 [4,19,25,[35][36][37] ) and opened (M 4 T 8 [38][39][40][41][42][43] ) structure even more scant. [5] Cage-like derivatives have driven much attention due to specific physicochemical properties (governed by the nature of their silicate rigid core and by the number and type of functional groups attached to it) affecting directions of their broad applications from material chemistry to medicine.…”

Vinyl‐Functionalized Silsesquioxanes and Germasilsesquioxanes

“…The first stage of our study was to develop efficient synthetic methods for the preparation of chlorovinylgermanes, which, in contrast to their silicon analogues, are not commercially available. Chloroarylvinyl‐ and chloroalkylvinylgermanes can be synthesized by the transmetalation of chlorogermanes with organotin reagents in the presence of a radical initiator . These reactions were performed in an inert gas atmosphere (Ar) through vacuum‐ line and standard Schlenk techniques owing to the sensitivity of the reagents.…”

“…Chloroarylvinyl-and chloroalkylvinylgermanes can be synthesized by the transmetalation of chlorogermanes with organotin reagents in the presence of a radical initiator. [19][20][21] These reactions were performed in an inert gas atmosphere (Ar) through vacuum-line and standard Schlenk techniques owing to the sensitivity of the reagents. The next step was the condensation of the POSS silanols and the respective chlorovinyl metalloids.…”

“…THF was dried with sodium benzophenone ketyl and freshly distilled before use. Vinylchlorogermanes: Chlorodimethylvinylgermane (1) [19] and dichloroethylvinylgermane (13) [20] were prepared according to the procedures reported previously.…”

“…Other studies have concerned theoretical calculations . Our group has synthesized fully condensed vinylgermasilsesquioxanes and dimethylvinylgermoxysilsesquioxanes as well as a double‐decker germasilsesquioxane and examined their reactivity in olefin cross‐metathesis . To date, there have been no reports on the synthesis of an incompletely condensed POSS with germanium atoms.…”