Hydrogen is one of the essential reactants in the chemical industry, though its generation from renewable sources and storage in a safe and reversible manner remain challenging. Formic acid (HCO2H or FA) is a promising source and storage material in this respect. Here, we present a highly active iron catalyst system for the liberation of H2 from FA. Applying 0.005 mole percent of Fe(BF4)2·6H2O and tris[(2-diphenylphosphino)ethyl]phosphine [P(CH2CH2PPh2)3, PP3] to a solution of FA in environmentally benign propylene carbonate, with no further additives or base, affords turnover frequencies up to 9425 per hour and a turnover number of more than 92,000 at 80°C. We used in situ nuclear magnetic resonance spectroscopy, kinetic studies, and density functional theory calculations to explain possible reaction mechanisms.
WOS:000295121500038
2011
333
6050
1733
1736
REVIEWED