Room‐Temperature Formate Ester Transfer Hydrogenation Enables an Electrochemical/Thermal Organometallic Cascade for Methanol Synthesis from CO2

The reduction of CO2 to synthetic fuels is a valuable strategy for energy storage. However, the formation of energy‐dense liquid fuels such as methanol remains rare, particularly under low‐temperature and low‐pressure conditions that can be coupled to renewable electricity sources via electrochemistry. Here, a multicatalyst system pairing an electrocatalyst with a thermal organometallic catalyst is introduced, which enables the reduction of CO2 to methanol at ambient temperature and pressure. The cascade methanol synthesis proceeds via CO2 reduction to formate by electrocatalyst [Cp*Ir(bpy)Cl]+ (Cp*=pentamethylcyclopentadienyl, bpy=2,2′‐bipyridine), Fischer esterification of formate to isopropyl formate catalyzed by trifluoromethanesulfonic acid (HOTf), and thermal transfer hydrogenation of isopropyl formate to methanol facilitated by the organometallic catalyst (H‐PNP)Ir(H)3 (H‐PNP=HN(C2H4PiPr2)2). The isopropanol solvent plays several crucial roles: activating formate ion as isopropyl formate, donating hydrogen for the reduction of formate ester to methanol via transfer hydrogenation, and lowering the barrier for transfer hydrogenation through hydrogen bonding interactions. In addition to reporting a method for room‐temperature reduction of challenging ester substrates, this work provides a prototype for pairing electrochemical and thermal organometallic reactions that will guide the design and development of multicatalyst cascades. The development and mechanistic understanding of room‐temperature transfer hydrogenation unlocks a multicatalyst cascade reaction strategy for the CO2 reduction to MeOH combining electrochemical and organometallic catalysis in the same reactor.