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Homoaromaticity in carbene intermediates

Freeman1, Pugh

  • 1Department of Chemistry, Oregon State University, Corvallis, Oregon 97331, USA.

The Journal of Organic Chemistry
|September 16, 2000
PubMed
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This study analyzes the stability and geometry of various singlet carbenes. Highly stabilized carbenes like 7-carbenanorbornene (4S) and 8-carbena-endo-tricyclo[3.2.1.0(2,4)]octane (5S) exhibit significant bending, unlike less stable counterparts.

Area of Science:

  • Computational Chemistry
  • Organic Chemistry
  • Quantum Chemistry

Background:

  • Carbenes are reactive intermediates with diverse electronic structures.
  • Understanding carbene stability and geometry is crucial for predicting reactivity.
  • Previous studies have explored carbene properties, but specific strained systems require further investigation.

Purpose of the Study:

  • To computationally analyze the isodesmic reaction energies for a series of singlet carbenes.
  • To investigate the geometric parameters of these carbenes and compare them to their triplet counterparts and parent hydrocarbons.
  • To determine the electronic properties, such as diamagnetic susceptibility and singlet-triplet energy differences, of these carbene systems.

Main Methods:

  • Density Functional Theory (DFT) calculations using the B3LYP functional.

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  • Utilized the 6-311+G(3df, 2p) basis set for geometry optimization and energy calculations.
  • Employed the 6-311+G(2d,p) basis set for calculating diamagnetic susceptibility exhaltations.

    • Main Results:

    • Singlet 7-carbenanorbornene (4S) and 8-carbena-endo-tricyclo[3.2.1.0(2,4)]octane (5S) show high stabilization energies (13.83 and 13.50 kcal/mol, respectively) with significant bending.
    • 3-carbenabicyclo[3.1.0]hexane (3S) exhibits minimal geometric change compared to its triplet or parent hydrocarbon.
    • 2-carbenabicyclooctadiene (7S) resembles an antihomoaromatic cation rather than a homoaromatic anion, with a negative stabilization energy (-3.01 kcal/mol).
    • Diamagnetic susceptibility exhaltations (Deltachi) varied significantly, with positive values for 4S (22.7) and 5S (26.0), indicating aromatic character, and negative values for 3S (-0.7) and 7S (-10.3).
    • Singlet-triplet energy differences (DeltaE(TS)) ranged from -4.0 to 27.1 kcal/mol, with some systems showing a preference for the singlet state.

    Conclusions:

    • The study highlights the significant impact of ring strain and electronic factors on carbene stability and geometry.
    • Specific carbene structures, like those in 4S and 5S, demonstrate unique bonding characteristics due to strong interactions with adjacent pi systems or strained rings.
    • The computational data provides valuable insights into the electronic nature and potential reactivity of these complex carbene systems, aiding in the design of novel organic molecules.