Performance enhancing additives for reusable ruthenium-triphos catalysts in the reduction of CO₂to dimethoxymethane

The direct access to dimethoxymethane (DMM) from CO2/H2 in MeOH is an attractive approach, but more active, selective, and robust catalyst systems are still desirable for an application of this system. Herein, we present the performance enhancing effect of additives on ruthenium-triphos catalyst systems for CO2 hydrogenation to DMM. In the presence of PPh3, functioning as both additional ligand and precursor for Lewis-acidic phosphonium salts, increased turnover numbers for DMM are achieved. Moreover, PPh3 significantly diminishes catalyst degradation via carbonylation to cationic [RuH(CO)2(triphos)]OTf, which remains an active species in the synthesis of DMM. Catalyst recycling over up to five runs with minimal loss in catalyst performance underlines the robustness of the system. Both, the recyclability of the system and the suppression of catalyst deactivation pathways encourage for application in sustainable continuous processes. This journal is