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Alcohol-Assisted Hydrogenation of Carbon Monoxide to Methanol Using Molecular Manganese Catalysts
Akash Kaithal1, Christophe Werlé1,2, Walter Leitner1,3
1Max Planck Institute for Chemical Energy Conversion, Stiftstrasse 34-36, 45470 Mülheim an der Ruhr, Germany.
Abstract:
Alcohol-assisted hydrogenation of carbon monoxide (CO) to methanol was achieved using homogeneous molecular complexes. The molecular manganese complex [Mn(CO)2Br[HN(C2H4P Pr2)2]] ([HN(C2H4P Pr2)2] = MACHO- Pr) revealed the best performance, reaching up to turnover number = 4023 and turnover frequency 857 h-1 in EtOH/toluene as solvent under optimized conditions (T = 150 °C, p(CO/H2) = 5/50 bar, t = 8-12 h). Control experiments affirmed that the reaction proceeds via formate ester as the intermediate, whereby a catalytic amount of base was found to be sufficient to mediate its formation from CO and the alcohol in situ. Selectivity for methanol formation reached >99% with no accumulation of the formate ester. The reaction was demonstrated to work with methanol as the alcohol component, resulting in a reactive system that allows catalytic "breeding" of methanol without any coreagents.
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