Dehydrogenation of formic acid catalyzed by magnesium hydride anions, HMgL2- (L = Cl and HCO2)

Abstract

A two step gas-phase catalytic cycle for the dehydrogenation of formic acid was established using a combination of experiments carried out on a quadrupole ion trap mass spectrometer and DFT calculations. The catalysts are the magnesium hydride anions HMgL2- (L = Cl and HCO2), which are formed from the formate complexes, HCO2MgL2-, via elimination of carbon dioxide under conditions of collision induced dissociation. This is followed by an ion-molecule reaction between HMgL2- and formic acid, which yields hydrogen and also reforms the formate complex, HCO2MgL2-. A kinetic isotope effect in the range 2.3-2.9 was estimated for the rate determining decarboxylation step by carrying out CID on the ..