Hydrogenation of CO 2 to Formate with a Highly Active Solid Ruthenium Phosphine

There is widespread interest in the hydrogenation of CO 2 to produce high‐energy substances such as formic acid. Herein, ruthenium trichloride was immobilized on porous phosphine polymers (Ru/KAPs‐Ph‐PPh 3 ) and gave excellent catalytic activity in the hydrogenation of CO 2 to produce formate. With the assistance of 1,8‐diazabicyclo[5.4.0]undec‐7‐ene (DBU), a high turnover number (TON) of up to 1470000 was obtained in 12 hours at 120 °C and a total pressure of 6 MPa (P(H 2 )/P(CO 2 )=1 : 1), with average TOFs of 122500 h −1 . Moreover, the catalyst can be easily recovered by filtration with acceptable catalytic effectiveness.