Herein, we report
an efficient synthesis and functionalization
of trifunctional open-cage-type silsesquioxanes. The method proposed
has been successfully applied for the synthesis of a library of incompletely
condensed silsesquioxanes with vinyldiorganosilyl functional groups,
which allows further modification. Detailed studies of hydrosilylation
of sterically different open-cage vinylsilsesquioxanes with a wide
spectrum of phenylsilanes catalyzed by platinum and rhodium compounds
are also reported. The influence of the reaction parameters, types
of reagents, and catalysts employed on the efficiency of the process
was examined. Optimization of the process based on the above results
permitted the design of a very attractive method for the synthesis
of multifunctionalized silsesquioxanes with excellent yields and regioselectivity.
Moreover, the results allowed the choice of the most efficient catalyst
whose application led to the selective formation of substituted open-cage
silsesquioxanes. These new compounds have been fully characterized
and studied in terms of their thermal properties.
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.
We report herein an efficient procedure for the synthesis of new polyhedral oligomeric silsesquioxane (POSS) derivatives as multifunctional reagents. This study concerns the incompletely condensed silsesquioxanes and germasilsesquioxanes with vinyl‐substituted silyl and germyl functional groups, which allow further modification. Furthermore, our experiments have been extended to the synthesis of a new subclass of completely condensed vinylgermasilsesquioxanes. These hybrid building blocks were obtained selectively within a few hours and isolated with excellent yields.
In this paper we present the synthesis of mixed bifunctional compounds of T8H8 silsesquioxane and spherosilicate (HSiMe2O)8Si8O12 derivatives via platinum‐catalyzed hydrosilylation of alkenylgermanes and olefins. To the best of our knowledge, this is the first literature example of bifunctional compounds with organogermyl functionalities. Eleven mixed systems with a variety of substituents (Si−H, alkyl, germyl, epoxy, and hydroxy) were prepared and fully characterized by NMR spectroscopy. Additionally, our research includes a real‐time FT‐IR study of the synthesis of these bifunctional compounds of the general formula (R)8‐m(GeR’3(CH2)n+2R)mSi8O12. and (R’’(CH2)2R)8‐m(GeR’3(CH2)2R)mSi8O12 where m∼4.
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