Ionic Liquids Effect on the Stability of 17-Electron Cation Product of the Electrochemical Oxidation of Cymantrene

The oxidative electrochemistry of cymantrene, CpMn(CO)₃ (1; Cp = [η⁵-C₅H₅]^–), was examined in ionic liquids (ILs) composed of anions of varying Lewis base properties. It was observed that the cyclic voltammetric responses strongly depended on the nucleophilic properties of the IL anion. Still, all observations are consistent with the initial formation of 1⁺ followed by an attack from the IL anion. In bis(trifluoromethylsulfonyl)amide [NTf₂]-based ILs, the process shows close to ideal electrochemical reversibility as the reaction between 1⁺ and [NTf₂] anion is very slow. On the other hand, in tetrafluoroborate and trifluoromethanesulfonate-based IL, the oxidation of 1 shows different levels of electrochemical reversibility with a marked sign of anion attack to 1⁺. In contrast, 1 exhibits an irreversible oxidation process in hexafluorophosphate-based IL. The reaction rate constants for the interaction of 1⁺ with the different IL anions were estimated by fitting the experimental data to digital simulations of the proposed mechanism. Besides, the use of [NTf₂]-based ILs as a supporting electrolyte in CH₂Cl₂ was also examined. The oxidation process of 1 shows a close to ideal electrochemical reversibility but low to non-chemical reversibility. This study illustrates the wide range of electrochemical environments available with ILs and demonstrates their limited utility for investigating the redox properties of metal carbonyl compounds. It also intends to warn the reader on how the IL media may influence an electrochemical study if care is not exercised.