The Pd(IV) complexes [Pd(dpk)Cl4] (1) and [Pd(dpk)2Cl2]+2 (2) have been shown to catalyze the electrochemical reduction of CO2 at a potential of -0.7 V (1) and -1.4 V (2) vs. Ag+/Ag. Ligation of CO2 with 1 and 2 is likely assisted through a mechanism similar to an enol-keto tautomerism with the ketone group on the dpk ligand. Electrocatalytic reduction of CO2 is demonstrated by cyclic voltammetric experiments. Compared to that seen for 1 & 2 in the absence of CO2, voltammograms obtained in the presence of CO2 show a substantial current enhancement on the cathodic scan associated with the loss of the primary oxidation wave on the anodic scan. Catalytic generation of CO2- radical anions followed by carbon-carbon bond formation was confirmed by catalytic reduction of 13CO2 followed by 13C-NMR analysis.

Electrocatalytic reduction of CO2 by [Pd(dpk)Cl4] and [Pd(dpk)2Cl2]+2

253rd National Meeting (2017)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.