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乙烯基取代的开笼倍半硅氧烷与苯基硅烷的合成及硅氢化反应:三官能团倍半硅氧烷的区域选择性合成

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

作者信息

Grzelak Magdalena, Januszewski Rafał, Marciniec Bogdan

机构信息

Faculty of Chemistry, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.

Center for Advanced Technology, Adam Mickiewicz University in Poznań, Uniwersytetu Poznańskiego 10, 61-614 Poznań, Poland.

出版信息

Inorg Chem. 2020 Jun 1;59(11):7830-7840. doi: 10.1021/acs.inorgchem.0c00947. Epub 2020 May 21.

DOI:10.1021/acs.inorgchem.0c00947
PMID:32436707
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7588036/
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.

摘要

在此,我们报道了三官能团开笼型倍半硅氧烷的高效合成及功能化。所提出的方法已成功应用于合成一系列具有乙烯基二有机硅烷基官能团的不完全缩合倍半硅氧烷,这使得进一步修饰成为可能。本文还报道了在铂和铑化合物催化下,空间结构不同的开笼型乙烯基倍半硅氧烷与多种苯基硅烷的硅氢加成反应的详细研究。考察了反应参数、所用试剂类型和催化剂对该过程效率的影响。基于上述结果对该过程进行优化,从而设计出一种极具吸引力的方法,用于合成具有优异产率和区域选择性的多官能化倍半硅氧烷。此外,这些结果有助于选择最有效的催化剂,其应用导致选择性地形成取代的开笼型倍半硅氧烷。这些新化合物已得到充分表征,并对其热性能进行了研究。

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