Reaction Mechanisms of CO2 Reduction to Formaldehyde Catalyzed by Hourglass Ru, Fe, and Os Complexes: A Density Functional Theory Study

The reaction mechanisms for the reduction of carbon dioxide to formaldehyde catalyzed by bis(tricyclopentylphosphine) metal complexes, [RuH2(H2)(PCyp3)2] (1Ru), [FeH2(H2)(PCyp3)2] (1Fe) and [OsH4(PCyp3)2] (1Os), were studied computationally by using the density functional theory (DFT). 1Ru is a recently reported highly efficient catalyst for this reaction. 1Fe and 1Os are two analogues of 1Ru with the Ru atom replaced by Fe and Os, respectively. The total free energy barriers of the reactions catalyzed by 1Ru, 1Fe and 1Os are 24.2, 24.0 and 29.0 kcal/mol, respectively. With a barrier close to the experimentally observed Ru complex, the newly proposed iron complex is a potential low-cost catalyst for the reduction of carbon dioxide to formaldehyde under mild conditions. The electronic structures of intermediates and transition states in these reactions were analyzed by using the natural bond orbital theory