Direct Synthesis of Methyl Formate from CO 2 With Phosphine‐Based Polymer‐Bound Ru Catalysts

Methyl formate was produced in one pot through the hydrogenation of CO 2 to formic acid/formate followed by an esterification step. The route offers the possibility to integrate renewable energy into the fossil‐based chemical value chain. In this work, a phosphine‐polymer‐anchored Ru complex was shown to be an efficient solid catalyst for the direct hydrogenation of CO 2 to methyl formate. The 1,2‐bis(diphenylphosphino)ethane‐like polymer presented the highest activity with a turnover number (TON) of up to 3401 at 160 °C. The reaction parameters were systemically investigated to optimize the reaction towards the formation of methyl formate. This catalyst could be reused seven times without a significant decrease in activity. Evolution of the catalytic Ru center during the reaction was revealed, and a possible reaction mechanism was proposed.