Dehydrogenation of formic acid to CO2 and H2 by manganese(I)–complex: Theoretical insights for green and sustainable route

In this work, a detailed computational study on a recently synthetized Mn(I)-dependent complex [(tBuPNNOP)Mn(CO)2 ]+ is reported. This species promotes the dehydrogenation of formic acid to carbon dioxide and hydrogen. The here proposed catalytic cycle proceeds through the formation of stabilized adduct between [(tBuPNNOPtBu)Mn(CO)2 ]+ and formate and the progressive release of CO2 and H2, mediated by the presence of trimethylamine. In order to evaluate the influence of the environment on the catalytic activity, different solvents have been taken into account. The computed barriers and the geometrical parameters account well for the available experimental data, confirming the robustness of the complex and reproducing its good catalytic performance. Outcomes from the present investigation can stimulate further experimental works in the design of new more efficient catalysts devoted to H2 production.