Hydrosilanes are convenient reductants for a large variety of organic oxygenated substrates and they have been successfully applied in the conversion of bio-based materials and CO2. Hydrosilanes are however produced via energy intensive processes and they generate, after use, silicon oxides wastes such as siloxanes, which are difficult to recycle. These limitations call for the development of catalytic processes able to transform Si-O bonds in siloxanes into Si-H hydrides. Previous reports have shown that chlorosilanes can be prepared from siloxanes by treatment with HCl. Catalytic methods that would convert Si-X linkages, and more precisely Si-Cl linkages, into Si-H hydrides are thus particularly attractive. We report here an efficient hydrogenolysis of chlorosilanes using [(tBuPOCOP)IrHCl] complex in mild conditions with selective formation of hydrosilanes in high yields (up to 79 %). These results represent an important step forward compared to the only example of hydrogenolysis of Si-Cl bonds (7 %) reported by Shimada. This very good performance was driven by the use of guanidine bases and have been rationalized based on NMR investigations and DFT calculations.

Catalytic hydrogenolysis of halogenosilanes to hydrosilanes using an iridium pincer complex

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.