Mn(III) O^N^O Complexes as Water‐tolerant and Environmentally Benign Catalysts for Polyurethane Foam Synthesis

Abstract Polyurethanes are synthesized on industrial scale by the reaction of diisocyanates with diols in the presence of catalysts which are commonly based on tin complexes and amines. However, due to the toxicity and volatility of these tin catalysts and amines, there is the need to develop new catalysts that are more environmentally benign. Herein, we report the synthesis of O^N^O pincer‐ligated Mn(III) and Fe(III) complexes that serve as suitable catalysts for urethane formation and are stable to hydrolysis as predicted by computations and observed experimentally. The O^N^O pincer scaffold is vital to the activity of these catalysts, simultaneously ensuring increased solubility in the reaction medium as well as providing a stable framework upon dissociation of co‐ligands in the catalytic cycle. In silico mechanistic investigations for urethane formation show that the stabilization of active species in square‐planar geometries enabled by these O^N^O ligands permit the simultaneous coordination of alcohol and isocyanate in suitable configuration at the metal center.