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.

A manganese–salen complex is shown to be effective in catalyzing the dehydrogenative coupling of hydroxyl groups with hydrosilane.

Recently, polycarbonates have attracted considerable research interest because of their potential biodegradability and sustainability. Here, we present a direct route for the synthesis of polycarbonates and poly(ether carbonate)s from carbon dioxide (CO₂) and diols, promoted by Cs₂CO₃ and CH₂Cl₂ under 1 atm of CO₂. Quantitative conversion of diols and polymers with up to 11 kg/mol molecular weight could be obtained. While benzylic diols lead to predominantly carbonate linkage, aliphatic diols result in the incorporation of the methylene unit of CH₂Cl₂ that produces poly(ether carbonate)s. Both primary and secondary diols have been successfully incorporated into the polymer chain.