Theoretica chimica acta

, Volume 45, Issue 4, pp 283–300 | Cite as

On the excited states ofp-quinones and an interpretation of the photocycloaddition ofp-quinones to alkenes

  • Nigel J. Bunce
  • Joan E. Ridley
  • Michael C. Zerner
Original Investigations

Abstract

A theoretical investigation is made of the electronic states ofp-benzoquinone (PBQ), methyl substituted PBQ's and 1,4-naphthoquinone (NQ). In accord with experiment, the lowest triplet state of PBQ is calculated to be3B 1g (n, π*), while that for duroquinone (DQ) is3B 3g (π, π*). The electron densities of these states are consistent with the hypothesis that3n, π* states lead to oxetan formation and3π, π* states to cyclobutanes. It is predicted that trimethyl PBQ might form both adducts, as the two states are calculated to be nearly degenerate.

The photochemistry of NQ is more complex. The lowest excited triplet state is calculated to be ofn, π* symmetry, in accord with experiment; however, several other states are predicted near in energy, and the photochemistry cannot be rationalized unambiguously.

Key words

p-Quinones, photocycloaddition with alkenes Electronic structure ofp-quinones Oxetans from3n, π* states ofp-quinones Cyclobutanes from3π, π* states ofp-quinones Spectra of quinones 

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Copyright information

© Springer-Verlag 1977

Authors and Affiliations

  • Nigel J. Bunce
    • 1
  • Joan E. Ridley
    • 1
  • Michael C. Zerner
    • 1
  1. 1.Guelph Waterloo Centre for Graduate Work in Chemistry, Dept. of ChemistryUniversity of GuelphGuelphCanada

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