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含硅烷的硼倍半硅氧烷:合成方法及意外的重排反应

Silane-Bearing Borasilsesquioxanes: Synthetic Protocol and Unsuspected Redistribution Reactions.

作者信息

Frydrych Miłosz, Sztorch Bogna, Brząkalski Dariusz, Pakuła Daria, Przekop Robert E, Srishailam Kanugula, Reddy Byru Venkatram, Marciniec Bogdan

机构信息

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

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

出版信息

Chempluschem. 2023 Jan;88(1):e202200295. doi: 10.1002/cplu.202200295.

Abstract

The presented work is a continuation of research on the reactivity of unsaturated borasilsesquioxanes under the conditions of common organometallic transformations. The catalytic hydrosilylation reaction with silanes, siloxanes and silsesquioxanes in presence of platinum catalyst was explored. The majority of the products were obtained in high yields (>90 %) and their structures were confirmed and characterized by spectroscopy and spectrometry, i. e. NMR and MALDI-TOF-MS. The most significant segment of the work is research on the spontaneous redistribution reaction of the alkoxy group from silane to borane moiety occurring in the obtained products, not being limited to the heterosilsesquioxane chemistry, however. The products were confirmed using GC-MS, ESI-MS methods and B3LYP exchange-correlation, in order to ascertain formation of the silicon-boron hybrid molecule.

摘要

本文所述工作是对不饱和硼倍半硅氧烷在常见有机金属转化条件下反应活性研究的延续。探索了在铂催化剂存在下与硅烷、硅氧烷和倍半硅氧烷的催化硅氢加成反应。大多数产物的产率很高(>90%),其结构通过光谱学和光谱法,即核磁共振(NMR)和基质辅助激光解吸电离飞行时间质谱(MALDI-TOF-MS)得到确认和表征。该工作最重要的部分是对所得产物中发生的烷氧基从硅烷部分自发重分布到硼烷部分的反应进行研究,不过这并不局限于杂化倍半硅氧烷化学领域。使用气相色谱 - 质谱联用(GC-MS)、电喷雾电离质谱(ESI-MS)方法以及B3LYP交换相关方法对产物进行了确认,以确定硅 - 硼杂化分子的形成。

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