Tunable Ruthenium Catalytic System for the Hydrogenation of Urea Derivatives

The hydrogenation of urea derivatives has been widely investigated as an intermittent route for utilizing CO 2 ; however, most studies in a given catalytic system are limited to producing only one type of product. We report herein a ruthenium catalytic system that enables selective semi‐hydrogenation to yield the more reactive formamides or complete hydrogenation to methanol, and this switch in product distribution can be achieved simply by controlling the reaction conditions. ESI–MS characterization and control experiments indicate that the formation and interconversion of active Ru─H and inactive Ru─CO complexes play a key role in switching product distribution. We hope these findings will provide a controllable strategy for product formation in the field of urea derivative hydrogenation.