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The electronic structure of 5-methylhexa-1,2,4-triene-1,3-diyl, the first representative of highly delocalized triplet ethynylvinylcarbenes, from ESR spectroscopy data and quantum chemical calculations

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Abstract

The ESR spectrum of the first representative of highly conjugated triplet ethynylvinylcarbenes, 5-methylhexa-1,2,4-triene-1,3-diyl (1), was recorded in solid argon matrix. The zero-field splitting (ZFS) parameters of carbene 1 (D = 0.5054±0.0006 cm−1 and E = 0.0045±0.0002 cm−1) determined from the experimental ESR spectrum are in between the corresponding parameters of ethynylcarbene C3H2 (2) and vinylcarbene C3H4 (3): D(3) < D(1) < D(2) and E(2) < E(1) < E(3). Quantum chemical calculations of the ZFS parameters of 1, 2, and 3 have been carried out for the first time using two DFT-based approaches, RODFT and UDFT. An analysis of the experimental and theoretical ZFS parameters shows that carbene 1 is characterized by a greater extent of delocalization of the spin density of unpaired electrons than carbenes 2 and 3. The characteristic structural fragments of carbene 1 possess the principal features of the electronic structure of both ethynylcarbene (2) and vinylcarbene (3), respectively. Magnetic spin-spin interactions are identical in carbenes 1 and 2. The dominant contribution to D in 1 and 2 results from the one-center spin-spin interactions on carbon atoms in the propynylidene group, which are subjected to strong spin polarization.

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Authors and Affiliations

  1. Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432, Chernogolovka, Moscow Region, Russian Federation

    E. Ya. Misochko, A. V. Akimov, A. A. Masitov, D. V. Korchagin & S. M. Aldoshin

  2. N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 119991, Moscow, Russian Federation

    S. E. Boganov, K. N. Shavrin, V. D. Gvozdev, M. P. Egorov & O. M. Nefedov

Authors
  1. E. Ya. Misochko
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  2. A. V. Akimov
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  3. A. A. Masitov
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  4. D. V. Korchagin
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  5. S. M. Aldoshin
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  6. S. E. Boganov
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  7. K. N. Shavrin
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  8. V. D. Gvozdev
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  9. M. P. Egorov
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  10. O. M. Nefedov
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Correspondence to E. Ya. Misochko or S. E. Boganov.

Additional information

Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2138–2145, November, 2011.

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Misochko, E.Y., Akimov, A.V., Masitov, A.A. et al. The electronic structure of 5-methylhexa-1,2,4-triene-1,3-diyl, the first representative of highly delocalized triplet ethynylvinylcarbenes, from ESR spectroscopy data and quantum chemical calculations. Russ Chem Bull 60, 2180–2187 (2011). https://doi.org/10.1007/s11172-011-0336-z

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  • DOI: https://doi.org/10.1007/s11172-011-0336-z

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