Supporting Information Table of Contents I. Materials II. Electrochemical data III. VDD charge analysis of cations IV. 13C NMR chemical shifts (ppm) of imidazolium NTf2 salts in CD3CN V. Stability of *CO2 ¯ vs free CO2 anion radical in acetonitrile VI. Interaction of C2-proton and C4, C5-protons of MM with Au-CO2 ¯ VII. Activation energy analysis for isomerization step VIII. Notes on the initial act of the electrode IX. Inverse kinetic isotope effect estimated from frequency calculations X. Extra notes on inverse kinetic isotope effect XI. Synthetic procedures XII. Copies of 1H, 13C, and 19F NMR spectra XIII. Computational methods
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