Dissociative electron transfer to haloacetonitriles. An example of the dependency of in-cage ion-radical interactions upon the leaving group

The reductive cleavage of the haloacetonitriles (Cl, Br, I) in DMF provides additional examples of the formation of a fragment cluster upon dissociative electron transfer, which is able to survive in this polar solvent thanks to the electron-withdrawing character of the cyano group. The remarkable sensitivity of the activation energy to small changes of the interaction energies allows, with help of the \u201csticky\u201d dissociative electron-transfer model, the precise determination of interaction energies down to a few millielectronvolts from the cyclic voltammetric data. The interaction energy rapidly decreases from Cl to Br and to I, correlated with the increase of the halide radius. These observations add to the previously gathered evidence to confirm the existence of such interactions and to highlight their electrostatic character. This is further corroborated by the quantum chemical computation of the potential energy profiles, which exhibit a long-distance energy minimum. This revisiting of the notion of \u3c3-ion radicals and of their status in a polar medium makes them appear as an electrostatic radical-ion pair rather than covalently bound molecules. Their stability is a function of the Lewis acid-base properties of both the radical and the leaving ion and is strongly influenced by the nature of the solvent

Homogeneous electron transfer catalysis of the electrochemical reduction of carbon dioxide. Do aromatic anion radicals react in an outer-sphere manner?

Electrochemically generated anion radicals of aromatic nitriles and esters possess the remarkable property to reduce carbon dioxide to oxalate with negligible formation of carboxylated products. They may thus serve as selective homogeneous catalysts for the reduction of CO2 in an aprotic medium. The catalytic enhancement of the cyclic voltammetric peaks of these catalysts is used to determine the rate constant of the electron transfer from these aromatic anion radicals to CO2 as a function of the catalyst standard potential. Substituted benzoic esters allowed a particularly detailed investigation of the resulting activation-driving force relationship. Using 14 different catalysts in this series made it possible to finely scan a range of reaction standard free energies of 0.4 eV. Detailed analysis of the resulting data leads to the conclusion that the reaction is not a simple outer-sphere electron transfer. It rather consists in a nucleophilic addition of the anion radical on CO2, forming an oxygen (or nitrogen for the nitriles)- carbon bond, which successively breaks homolytically, generating the parent ester (or nitrile) and the anion radical of CO2, which eventually dimerizes to oxalate

Mechanism of the electrochemical reduction of carbon dioxide at inert electrodes in media of low proton availability

Direct electrolysis of CO2 in DMF at an inert electrode, such as mercury, produces mixtures of CO and oxalate, whereas electrolysis catalysed by radical anions of aromatic esters and nitriles produces exclusively oxalate in the same medium. Examination of previous results concerning the direct electrochemical reduction and the reduction by photoinjected electrons reveals that there are no significant specific interactions between reactant, intermediates and products on the one hand, and the electrode material on the other, when this is Hg or Pb. These observations and a systematic study of the variations of the oxalate and CO yields with temperature and CO2 concentration, allow the derivation of a consistent mechanistic model of the direct electrochemical reduction. It involves the formation of oxalate from the coupling of two CO2 radical anions in solution. CO (and an equimolar amount of carbonate) is produced by reduction at the electrode of a CO2-CO2= adduct, the formation of which, at the electrode surface, is rendered exothermic by non-specific electrostatic interactions