Versatile Manganese Catalysis for the Synthesis of Poly(silylether)s from Diols and Dicarbonyls with Hydrosilanes

Poly(silylether)s are interesting materials because of their degradation property under hydrolytic conditions and have been prepared via hydrosilylation polymerization from dicarbonyl and hydrosilanes, and via dehydrogenative cross-coupling of diols and hydrosilanes under catalytic conditions. Here, we present a manganese-salen compound based on an inexpensive and nontoxic metal that could effectively catalyze both polymerization reactions with hydrosilane. A series of poly(silylether)s containing various aliphatic and aromatic backbones have been synthesized from diol and dicarbonyl substrates. Moderate to high yields of polymers with number-average molecular weights up to 15 kg/mol are obtained. Because of the dual activity of the manganese catalyst, unsymmetrical substrates with mixed functional groups, such as p -hydroxybenzaldehyde, p -hydroxy benzylalcohol, and 3-(4-hydroxyphenyl)-1-propanol, have been employed to afford poly(silylether)s with multiple silicon connectivity in the main chain.