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Published on: April 10, 2015
Carbon Dioxide Hydrogenation to Formate Catalyzed by a Neutral, Coordinatively Saturated Tris-Carbonyl Mn(I)-PNP
Sylwia Kostera1, Gabriele Manca1, Luca Gonsalvi1
1Istituto di Chimica dei Composti Organometallici (ICCOM), Consiglio Nazionale delle Ricerche (CNR), Via Madonna del Piano 10, 50019, Sesto, Fiorentino (Florence), Italy.
Abstract:
CO2 catalytic hydrogenation to formate was achieved (TONmax =ca. 3800) in the presence of the neutral, halide-free, coordinatively saturated tris(carbonyl) manganese pincer-type complex [Mn(PNP)(CO)3 ], bearing a diarylamido pincer-type PNP ligand, using DBU as base and LiOTf as Lewis acid additive, under mild reaction conditions (60 bar, 80 °C). DFT calculations suggest that the precatalyst activation key step occurs by intermolecular, base assisted dihydrogen heterolytic splitting rather than by the expected ligand-assisted intramolecular MLC-type mechanism.
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