Facile One-Pot Preparation of Organotin-Oxometalate Polymers for Efficient Synthesis of Dimethyl Carbonate from CO2

Dimethyl carbonate (DMC) is an important synthetic intermediate with widespread applications in the chemical industry. In recent years, the one-step conversion of CO2 into DMC has gained significant attention, but the development of an efficient catalytic system remains a considerable challenge to realize this process. Herein, a series of organotin-oxometalate coordination polymers were developed for DMC synthesis from CO2 and methanol without any solvent/dehydrating agent, and it was found that the metal complexes displayed excellent catalytic performances, especially (nBu3Sn)2MoO4 with the n-butyl group (Bu) was very active, and a high DMC yield (15.7 mmol gcat–1) and high TON value (3.90) were achieved under mild conditions, which was remarkably higher than the recently reported catalytic systems. Moreover, the polymer was highly stable and easy to be recycled with no significant activity loss. Experimental and in situ FT-IR studies revealed that the synergetic catalysis of [Bu3Sn]+ and [MoO4]2– to active CO2 and methanol was the key reason for improved catalytic activity. This study offers a promising strategy for the efficient synthesis of organic carbonates catalyzed by metal complexes to realize better CO2 utilization.