Electrocatalytic CO 2 Conversion to Oxalate by a Copper Complex

Global warming concern has dramatically increased interest in using CO2 as a feedstock for preparation of value-added compounds, thereby helping to reduce its atmospheric concentration. Here, we describe a dinuclear copper(I) complex that is oxidized in air by CO2 rather than O2; the product is a tetranuclear copper(II) complex containing two bridging CO2-derived oxalate groups. Treatment of the copper(II) oxalate complex in acetonitrile with a soluble lithium salt results in quantitative precipitation of lithium oxalate. The copper(II) complex can then be nearly quantitatively electrochemically reduced at a relatively accessible potential, regenerating the initial dinuclear copper(I) compound. Preliminary results demonstrate six turnovers (producing 12 equivalents of oxalate) during 7 hours of catalysis at an applied potential of -0.03 volts versus the normal hydrogen electrode.