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Russian Chemical Bulletin

, Volume 43, Issue 10, pp 1710–1714 | Cite as

Electron-transfer induced haptotropic isomerization of fluorenylmanganesetricarbonyl complexes: electrocatalytic and chain mechanisms

  • S. V. Kukharenko
  • L. N. Novikova
  • V. V. Strelets
  • N. A. Ustynyuk
  • A. I. Yarmolenko
Organometallic Chemistry

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 isomerization12 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 isomerization12 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.

Key words

fluorenylmanganesetricarbonyl haptotropic rearrangements electron-transfer induced reactions electrocatalysis cyclic voltammetry 

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Copyright information

© Plenum Publishing Corporation 1995

Authors and Affiliations

  • S. V. Kukharenko
    • 1
  • L. N. Novikova
    • 2
  • V. V. Strelets
    • 1
  • N. A. Ustynyuk
    • 2
  • A. I. Yarmolenko
    • 1
  1. 1.Institute of Chemical Physics in ChernogolovkaRussian Academy of SciencesChernogolovka, Moscow RegionRussian Federation
  2. 2.A. N. Nesmeyanov Institute of Organoelement CompoundsRussian Academy of SciencesMoscowRussian Federation

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