Cobalt-Catalyzed Hydrosilylation of Carbon Dioxide to the Formic Acid, Formaldehyde, and Methanol Level—How to Control the Catalytic Network?

[Image: see text] The selective hydrosilylation of carbon dioxide (CO(2)) to either the formic acid, formaldehyde, or methanol level using a molecular cobalt(II) triazine complex can be controlled based on reaction parameters such as temperature, CO(2) pressure, and concentration. Here, we rationalize the catalytic mechanism that enables the selective arrival at each product platform. Key reactive intermediates were prepared and spectroscopically characterized, while the catalytic mechanism and the energy profile were analyzed with density functional theory (DFT) methods and microkinetic modeling. It transpired that the stepwise reduction of CO(2) involves three consecutive catalytic cycles, including the same cobalt(I) triazine hydride complex as the active species. The increasing kinetic barriers associated with each reduction step and the competing hydride transfer steps in the three cycles corroborate the strong influence of the catalyst environment on the product selectivity. The fundamental mechanistic insights provide a consistent description of the catalytic system and rationalize, in particular, the experimentally verified opportunity to steer the reaction toward the formaldehyde product as the chemically most challenging reduction level.