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Introduction of Boron Functionalities into Silsesquioxanes: Novel Independent Methodologies.

Owing to their versatile application possibilities, silsesquioxanes (SQs) are of considerable interest for creating hybrid inorganic-organic materials. In this report, two novel and independent strategies for the direct attachment of boron functionalities to silsesquioxanes are presented. Encouraged by our previous work concerning the synthesis of borasiloxanes through the catalyst-free dehydrogenative coupling of silanols and boranes, we decided to apply our method to a synthesis of various boron-functionalized silsesquioxanes. During our tests, we also investigated the activity of scandium(III) triflate, which we have previously used as an excellent catalyst for the obtaining of Si-O-Si and Si-O-Ge moieties. As a result, we also discovered a novel approach for the O-borylation of Si-OH groups in silsesquioxanes with allylborane. Both routes are highly chemoselective and efficiently lead to the obtaining of Si-O-B moiety under air atmosphere and at room temperature.