As one of the possible products of CO2 reduction, carbon monoxide is particularly interesting due to a high number of possibilities for further processing as C1-building block. Due to the high overpotential of electrochemical CO2 reduction and numerous possible reaction pathways, a selective cathodic transformation of CO2 to CO is not trivial.[1-2] In this context, considerable progress has been recently made with homogeneous electrocatalysts.[3-5] However, many of the methods reported thus far require either precious metal centers such as Re or Ru, excess amounts of a proton donor such as trifluoroethanol or phenol and/or ligands with limited availability such as porphyrine analogues. Herein we report a protocol, where robust and easy-to-synthesize (cyclopentadienone)iron-tricarbonyl complexes are used for the selective electroreduction of CO2 to CO in the absence of proton donors. Electroanalytical experiments were carried out in order to characterize the complexes and to evaluate their catalytic behavior. These experiments show high turnover frequencies and a remarkable influence of the ligand substitution and the solvent on the catalytic performance. The application in bulk electrolysis under optimized conditions rendered excellent Faradaic yields and turnover numbers. Along with the catalytic performance, possible mechanisms are discussed based on voltammetric data and DFT calculations.

Electrocatalytic reduction of CO2 using cyclopentadienone iron complexes

253rd National Meeting (2017)

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