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IR Spectroscopic study of matrix-isolated free allyl radicals and analysis of vibrational spectra and structure of π-allyl organometallic compounds

  • Physical Chemistry
  • Published:
Bulletin of the Academy of Sciences of the USSR, Division of chemical science Aims and scope

Conclusions

  1. 1.

    By the technique of matrix isolation of products from the vacuum pyrolysis of 1,5-hexadiene-d10, the IR spectrum of the free allyl radical C3D5 has been obtained for the first time.

  2. 2.

    On the basis of the IR spectra of the C3H5 and C3D5 radicals, vibrational frequencies of the allyl radical have been calculated, and the bands have been assigned to the normal vibrations.

  3. 3.

    A systematic comparison has been made of the vibrational frequencies of the allyl radical and the Π-allyl ligand in the composition of organometallic compounds. It has been established that the frequencies of out-of-plane vibrations ρw(CH2), ρt(CH2), and ρ(CH) are substantially higher for the Π-allyl ligand; the frequencies of vibrations taking place in the plane of the allyl fragment are little different for the two cases. A new assignment has been proposed for a number of frequencies in the spectra of Π-allyl complexes.

  4. 4.

    The system of bonds

    for the allyl radical is characterized by relatively low frequencies of stretching vibrations and the force constant

    5. 8 mdyne/Å. The values of νs(CCC) and νas(CCC) show that upon formation of a Π-allyl complex, there is no loosening of the carbon-carbon bonds of the ligand, in contrast to Π-complexes of unsaturated compounds.

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Authors and Affiliations

  1. N. D. Zelinskii Institute of Organic Chemistry, Academy of Sciences of the USSR, Moscow

    A. K. Mal'tsev, V. A. Korolev & O. M. Nefedov

Authors
  1. A. K. Mal'tsev
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  2. V. A. Korolev
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  3. O. M. Nefedov
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Additional information

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 555–568, March, 1984.

The authors wish to express their gratitude to V. N. Khabashesk for assistance in the synthesis of the CD2=CDCD2Cl, to N. D. Kagramanov for taking the mass spectrum of the sample of C6D10, and to É. G. Baskir for assistance in performing the vibrational calculations.

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Mal'tsev, A.K., Korolev, V.A. & Nefedov, O.M. IR Spectroscopic study of matrix-isolated free allyl radicals and analysis of vibrational spectra and structure of π-allyl organometallic compounds. Russ Chem Bull 33, 510–521 (1984). https://doi.org/10.1007/BF00995688

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  • DOI: https://doi.org/10.1007/BF00995688

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