Synthesis of (Multi)Silylalkynyl-Substituted Silsesquioxanes Obtained via Silylative Coupling Reaction

Abstract

In the view of the fact that catalytic routes to design functionalized silsesquioxanes are currently of high importance, herein we report the effective functionalization procedure to obtain mono-, di-, and tetrasilylalkynylsubstituted silsesquioxanes of cubic T 8 and DDSQ type. The synthetic methodology is based on Ru-hydride complex that turned out to be an efficient catalyst for silylative coupling of ethynylsiloxysubstituted silsesquioxanes with vinylsilanes resulted in their silylalkynyl analogues. The ethynylsiloxysubstituted double-decker silsesquioxanes have been noted to be reactive in this process for the first time. A series of novel compounds were obtained, isolated, and characterized. Due to the presence of silylalkynyl moieties, they constitute an interesting family of Si−O−Si-based unique structures with potential applications.

Synthesis of Alkynylsilanes: A Review of the State of the Art

“…Subsequently, Marciniec and his co-workers expanded the application of this method to analogous germanium compounds and the functionalization of silsesquioxanes. [212][213][214]…”

Synthesis and Hydrosilylation of Vinyl-Substituted Open-Cage Silsesquioxanes with Phenylsilanes: Regioselective Synthesis of Trifunctional Silsesquioxanes

“…The research area focused on silsesquioxanes is one of the most dynamically developing in the chemistry of silicon compounds. Polyhedral oligomeric silsesquioxanes (POSSs) are characterized by structural diversity and the possibility of attachment of a variety of functional groups that significantly change their reactivity and solubility. − These properties can be easily modified by the introduction of various substituents by using a wide spectrum of catalytic and noncatalytic chemical reactions (e.g., Heck coupling, − metathesis, − silylative coupling, − and many others , ). Among all of the above-mentioned methods, hydrosilylation of olefins (the addition of Si–H bonds to unsaturated systems, e.g., CC bonds, resulting in the formation of a C–Si bond) is one of the fundamental processes used in industry and laboratory.…”

B(C6F5)3-Catalyzed Dehydrocoupling of POSS Silanols with Hydrosilanes: A Metal-Free Strategy for Effecting Functionalization of Silsesquioxanes

“…Over the past few years, research on silsesquioxanes has been extended . Several catalytic methods were developed. − Nevertheless, all mentioned catalytic approaches employ expensive metal catalysts and/or harsh conditions. Furthermore, some of these methodologies are limited to only one example due to the scarce availability of reagents required in the process (e.g., dihydrosilanes and trihydrosilanes) .…”