Abstract
The electrochemical reduction of (η6-C13H9)Mn(CO)3 (1, where C13H9—fluorenyl) has been studied in THF by cyclic voltammetry and preparative controlled potential electrolysis. One-electron reduction of1 to the corresponding 19-electron radical anion1.− is accompanied by the haptotropic isomerization of the latter to the radical anion (η5-C13H9)Mn(CO)3.− (2.−), which is oxidized at the electrode to neutral complex2. Electron-transfer induced isomerization1 →2 is an electrocatalytic process with current efficiency of 600%, which can be also promoted by catalytic amounts (≤20%) of the chemical reducing agents (benzophenone radical anion or sodium amalgam). If the reaction is chemically induced, the radical anion2.− is oxidized by initial complex1; as a result the electron-transfer induced isomerization1 →2 proceeds by a chain mechanism. The influence of the electronic state (18e−/19e−) of η6- and η5-fluorenyl complexes on the position of the equilibrium of the intra-ring haptotropic isomerization reaction is discussed.
Published Version
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