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Permethylated metallocenes as suitable models for the preparation of onium mono- and dications

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Abstract

Permethylated metallocenes of the iron subgroup (M = Fe, Ru, Os) have been considered as suitable models for preparing onium mono- and dications. EHM MO calculations of the charge, distribution in monocations of the type (C5Me5MC5Me4CH2)+, homoannular dications of the type [C5Me5MC5Me3(CH2)2]2+, and heteroannular dications of the type [(C5Me4CH2)2M)]2+ indicate that the positive charge is mostly localized at the metal atom (M = Ru, Os and, to a lesser degree, Fe). This fact was confirmed by X-ray structural studies and the data of IR,1H, and13C NMR spectroscopy, and electrochemistry. The reactivity of the monocations, in particular, interconversion of the odd-electron (17- and 19-electron) metallocenium radical cations and 18-electron metallocenyl carbocations has been studied. A M-C(α) σ-bond (M = Ru, Os) is realized in the mono- and dications. It has been suggested that the metallocenyl carbocations (M = Ru, Os) are in fact metallonium or metallocenonium cations (or dications).

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Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1701–1709, October, 1994.

We are grateful to the Uussian Ministry of Science and Technical for its Grant.

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Rybinskaya, M.I., Kreindlin, A.Z., Hoffmann, R. et al. Permethylated metallocenes as suitable models for the preparation of onium mono- and dications. Russ Chem Bull 43, 1605–1612 (1994). https://doi.org/10.1007/BF00703471

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Key words

  • onium mono- and dications
  • carbocations
  • permethylated metallocenes
  • EHM MO calculations
  • X-ray structural studies
  • IR
  • NMR spectra