Catalytic Synthesis of Oligosiloxanes Mediated by an Air Stable Catalyst, (C₆F₅)₃B(OH₂)

The utility of (C₆F₅)₃B(OH₂) as catalyst for the simple and environmentally benign synthesis of oligosiloxanes directly from hydrosilanes, is reported. This protocol offers several advantages compared to other methods of synthesizing siloxanes, such as mild reaction conditions, low catalyst loading, and a short reaction time with high yields and purity. The considerable H₂O-tolerance of (C₆F₅)₃B(OH₂) promoted a catalytic route to disiloxanes which showed >99% conversion of three tertiary silanes, Et₃SiH, PhMe₂SiH, and Ph₃SiH. Preliminary data on the synthesis of unsymmetrical disiloxanes (Si-O-Si') suggests that by modifying the reaction conditions and/or using a 1:1 combination of silane to silanol the cross-product can be favored. Intramolecular reactions of disilyl compounds with catalytic (C₆F₅)₃B(OH₂) led to the formation of novel bridged siloxanes, containing a Si-O-Si linkage within a cyclic structure, as the major product. Moreover, the reaction conditions enabled recovery and recycling of the catalyst. The catalyst was re-used 5 times and demonstrated excellent conversion for each substrate at 1.0 mol% catalyst loading. This seemingly simple reaction has a rather complicated mechanism. With the hydrosilane (R₃SiH) as the sole starting material, the fate of the reaction largely depends on the creation of silanol (R₃SiOH) from R₃SiH as these two undergo dehydrocoupling to yield a disiloxane product. Generation of the silanol is based on a modified Piers-Rubinsztajn reaction. Once the silanol has been produced, the mechanism involves a series of competitive reactions with multiple catalytically relevant species involving water, silane, and silanol interacting with the Lewis acid and the favored reaction cycle depends on the concentration of various species in solution.