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Tricarbonylchromium complexes with phenalene. Synthesis, structure, and thermal rearrangements

  • Organometallic Chemistry
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Russian Chemical Bulletin Aims and scope

Abstract

The reaction of phenalene with Cr(CO)3Py3/BF3·OEt2 afforded a mixture of two isomeric complexes, tricarbonyl(6a,7-9,9a,9b-·6-phenalene)chromium (1) and tricarbonyl(3a,6a,9b,4-6-·6-phenalene)chromium (2). Deprotonation of the mixture of compounds1 and2 followed by treatment with MeI, BunI, or D2O gave complexesexo-1-R-1 (3–5: R=Me (3), Bun (4), or D (5)). The molecular geometry of complex3 was established by X-ray structural analysis. Heating of complex5 in toluene or C6F6 at 90–110 °C resulted in redistribution of deuterium among positionsexo-1,endo-1, and 3 in the resulting complexes of types1 and2 via sigmatropic shifts of the H exo and H endo atoms in the nonaromatic ring as well asvia inter-ring migrations of the tricarbonylchromium group. In the case of3, the methyl label is distributed among positionsexo-1 and3 to form isomeric complexes with similar structures (exo-1-Me-2 (6), 3-Me-2 (7), and 3-Me-1 (8), respectively)via processes analogous to those observed in the case of isomerization of compound5 (except for migration of the H exo atom). The mechanisms of these rearrangements are discussed.

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Authors and Affiliations

  1. Department of Chemistry, M. V. Lomonosov Moscow State University, Vorob'evy Gory, 119899, Moscow, Russian Federation

    N. G. Akhmedov, E. A. Katsman, S. G. Malyugina, V. I. Mstislavsky, Yu. F. Oprunenko, V. A. Roznyatovsky & Yu. A. Ustynyuk

  2. A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813, Moscow, Russian Federation

    A. S. Batsanov & N. A. Ustynyuk

Authors
  1. N. G. Akhmedov
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  2. E. A. Katsman
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  3. S. G. Malyugina
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  4. V. I. Mstislavsky
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  5. Yu. F. Oprunenko
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  6. V. A. Roznyatovsky
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  7. Yu. A. Ustynyuk
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  8. A. S. Batsanov
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  9. N. A. Ustynyuk
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Additional information

Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1863–1880, October, 1997.

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Akhmedov, N.G., Katsman, E.A., Malyugina, S.G. et al. Tricarbonylchromium complexes with phenalene. Synthesis, structure, and thermal rearrangements. Russ Chem Bull 46, 1769–1786 (1997). https://doi.org/10.1007/BF02495134

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  • DOI: https://doi.org/10.1007/BF02495134

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