Oxidation of Hydrosilanes to Silanols by Peracetic Acid

Silanols are utilized extensively in the silicone industry both as intermediates and in formulated products where subsequent condensation is desired, such as moisture-cured sealants. More recently, silanols have attracted attention as versatile reagents in chemical synthesis. The development of selective routes to silanols is of longstanding interest and often proceeds via the oxidation or hydrolysis of hydrosilanes using transition-metal catalysts or stoichiometric oxidants. Transition-metal solutions often require costly catalysts that must be removed or recycled, while previously disclosed stoichiometric oxidants suffer from manufacturing, handling, and environmental issues that preclude their widespread adoption. In contrast, peracetic acid has found broad applications in water treatment, sterilization, and disinfection as a more sustainable alternative. Here, we report that peracetic acid is also an efficient and selective oxidant for a number of alkyl and aryl silanes as well as small molecule and polymeric hydrosilane-functional siloxanes. Computational modeling was also utilized to gain insight into the catalytic mechanism and observe the relative reactivities of different substrates and common oxidants.