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

Abstract

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.

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

“…unique physical and chemical properties are widely used in material science. [43,44] Also this time (the Si-O-Si bond formation), there are several established methods, which can be carried out in both stoichiometric [43,45,46] or catalytic manner. [47][48][49][50][51][52][53][54][55][56][57][58][59][60] To sum up, the vast majority of known O-silylation strategies is presented on Figure 1, including their main benefits and drawbacks.…”

Double-Decker Silsesquioxanes Self-Assembled in One-Dimensional Coordination Polymeric Nanofibers with Emission Properties

“…It should be also noted that DDSQb -containing Si–Ph groups revealed higher thermal stability than the methyl derivative ( DDSQa ), consistent with the literature. 64 , 65 The opposite order was observed after the DDSQ functionalization through Sonogashira coupling; nevertheless, the differences in the T d 5% values did not turn out to be significant for DDSQ_Ta-b as was observed for DDSQa-b . Most of the samples exhibited a bimodal decomposition mechanism; however, a multimodal degradation was observed for DDSQ_Tb and T in a nitrogen atmosphere, manifested by the appearance of two main peaks at DTG curves.…”

Hydrosilylation and hydroboration in a sustainable manner: from Earth-abundant catalysts to catalyst-free solutions

“…Undoubtedly, hydrosilylation is to the most useful and applicable reaction in organosilicon chemistry, being simultaneously one of the most important homogeneous processes in industry. 28 In spite of a multitude of efforts to replace noble metals as catalysts, it should be made clear that platinumbased systems are still the most useful for both large 29 and small-scale [30][31][32][33][34][35][36][37] productions of organosilicon derivatives, which were quite nicely summarized by Marciniec and coworkers. 38 However, an extremely high price of these catalysts and often also harsh reaction conditions have caused an extensive exploration of less expensive and milder alternatives.…”