Liberation of carbon monoxide from formic acid mediated by molybdenum oxyanions

Abstract

Multistage mass spectrometry experiments, isotope labelling and DFT calculations were used to explore whether selective decarbonylation of formic acid could be mediated by molybdate anions [(MoO3)x(OH)]− (x = 1 and 2) via a formal catalytic cycle involving two steps. In step 1, both molybdate anions undergo gas-phase ion-molecule reactions (IMR) with formic acid to produce the coordinated formates [(MoO3)x(O2CH)]− and H2O. In step 2, both coordinated formates [(MoO3)x(O2CH)]− undergo decarbonylation under collision-induced dissociation (CID) conditions to reform the molybdate anions [(MoO3)x(OH)]− (x = 1 and 2), thus closing a formal catalytic cycle. In the case of [MoO3(O2CH)]− an additiona..