Exploring the Electrochemistry of Iron Dithiolene and Its Potential for Electrochemical Homogeneous Carbon Dioxide Reduction

Abstract

In this work, the dithiolene complex iron(III) bis-maleonitriledithiolene [Fe(mnt)2] is characterised and evaluated as a homogeneous CO2 reduction catalyst. Electrochemically the Fe(mnt)2 is reduced twice to the trianionic Fe(mnt)23− state, which is correspondingly found to be active towards CO2. Interestingly, the first reduction event appears to comprise overlapping reversible couples, attributed to the presence of both a dimeric and monomeric form of the dithiolene complex. In acetonitrile Fe(mnt)2 demonstrates a catalytic response to CO2 yielding typical two-electron reduction products: H2, CO and CHOOH. The product distribution and yield were governed by the proton source. Operating with H2O as the proton source gave only H2 and CO as products, whereas using 2,2,2-trifluoroethanol gave 38 % CHOOH faradaic efficiency with H2 and CO as minor products.