Abstract
It has been shown by cyclic voltammetry in a THF medium in the temperature range from −70 °C to +20 °C that one-electron electrochemical reduction of (η6-C13H10)Cr(CO)3 (1) to the corresponding 19-electron anion radical (1 −) is accompanied by splitting off of a H atom to form the 18-electron carbon-centered anion (η6-C13H9)Cr(CO)3 (−2), which at room temperature undergoes intramolecular haptotropic isomerization to the metal-centered (η5-C13H9)Cr(CO)3 − (− 3) anion. The reversible one-electron reduction of3 − to the corresponding 19-electron radical dianion3 2.− induces η5→ η6 interannular isomerization. In contrast to the equilibrium shift to the η5-isomer in 18-electron complexes 2 and 3, in their 19-electron analogs the equilibrium is shifted to the η6-isomer.
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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 48–53, January, 1994.
This work was carried out with financial support from the Russian Foundation for Basic Research (no. 93-03-5209)
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Kukharenko, S.V., Novikova, L.N., Strelets, V.V. et al. Electron-transfer induced change of direction of interannular haptotropic isomerization of fluorenyltricarbonylchromium anions. Russ Chem Bull 43, 41–46 (1994). https://doi.org/10.1007/BF00699132
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DOI: https://doi.org/10.1007/BF00699132