Synthesis based on electrogenerated carbenes

4. Quantum-chemical investigation of dinitrocarbene generation in electrooxidation of dinitromethylides, and evaluation of reactivity of this species
  • V. A. Petrosyan
  • A. A. Fainzil'berg
  • M. E. Niyazymbetov
  • V. N. Solkan
Physical Chemistry

Conclusions

  1. 1.

    The MINDO/3 method has been used to calculate enthalpies in decomposition reactions of the dimethylsulfonium dinitromethylide cation radical in the gas phase; it has been shown that the most probable direction of decomposition leads to the formation of dinitrocarbene.

     
  2. 2.

    The MINDO/3 method has been used to calculate the geometric parameters and electronic structure of dinitrocarbene, and it has been shown that the singlet state is more favorable than the triplet state. It has been found that, in a series of singlet carbenes with electron-acceptor substituents, dinitrocarbene is the strongest electrophile.

     

Keywords

Enthalpy Geometric Parameter Carbene Cation Radical Triplet State 

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Literature cited

  1. 1.
    M. E. Niyazymbetov, V. A. Petrosyan, V. V. Semenov, and S. A. Shevelev, Izv. Akad. Nauk SSSR, Ser. Khim., No. 6, 1332 (1981).Google Scholar
  2. 2.
    V. A. Petrosyan, A. A. Fainzil'berg, S. A. Shevelev, et al., Izv. Akad. Nauk SSSR, Ser. Khim., No. 2, 356 (1989).Google Scholar
  3. 3.
    M. J. Dewar and R. G. Dougherty, The PMO Theory of Organic Chemistry, Plenum Press, New York (1975).Google Scholar
  4. 4.
    D. R. Stull, E. F. Westram, and G. C. Sinke, The Chemical Thermodynamics of Organic Compounds, Wiley, New York (1969).Google Scholar
  5. 5.
    V. V. Semenov, L. O. Atovmyan, N. I. Golovina, et al., Izv. Akad. Nauk SSSR, Ser. Khim., No. 4, 801 (1981).Google Scholar
  6. 6.
    T. L. Cottrell, The Strengths of Chemical Bonds, Academic Press, New York (1954).Google Scholar
  7. 7.
    K. Ya. Burshtein, Zh. Strukt. Khim.,28, 3 (1987).Google Scholar
  8. 8.
    Yu. A. Lebedev, E. A. Miroshnichenko, and Yu. K. Knobel', Thermochemistry of Nitro Compounds [in Russian], Nauka, Moscow (1970), p. 125.Google Scholar
  9. 9.
    R. Moss, Acc. Chem. Res.,13, 58 (1980).Google Scholar

Copyright information

© Plenum Publishing Corporation 1989

Authors and Affiliations

  • V. A. Petrosyan
    • 1
  • A. A. Fainzil'berg
    • 1
  • M. E. Niyazymbetov
    • 1
  • V. N. Solkan
    • 1
  1. 1.N. D. Zelinskii Institute of Organic ChemistryAcademy of Sciences of the USSRMoscow

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