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The Energetics of Halogenated Ethylenes (Ethynes) and 1,3-Butadienes (Butadiynes): A Computational and Conceptual Study of Substituent Effects and “Dimerization”

Croatian Chemical Society
Publication Date
  • Dienes
  • Diynes
  • Halogenated Compounds
  • Resonance (Conjugation) Energy
  • Isodesmic Reactions
  • Ab Initio Calculations
  • Chemistry
  • Physics


The energetics of ethylenes and 1,3-butadienes may be interrelated by the reaction: RHC=CH2 + H2C=CHR' → RHC=CH−CH=CHR' + H2. Shown earlier to be nearly enthalpically thermoneutral for a variety of hydrocarbon cases, we are now interested in the related energetics of halogenated alkenes and alkynes. Using quantum chemical calculations, we have studied this as recast as the isodesmic reactions: 2(H2C=CHX) + H2C=CH−CH=CH2 → p,q-di-X-1,3-butadiene + 2H2C=CH2 2(HC≡CX) + HC≡C−C≡CH → di-X-butadiyne + 2HC≡CH. Here p,q- = 1,3-; 1,4- and 2,3- with X = F, Cl, Br, and I. The halogen and location-dependent deviations from near enthalpic thermoneutrality are discussed.

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