Structural Chemistry

, Volume 28, Issue 3, pp 597–605 | Cite as

Halodiazirines and halodiazo compounds: a computational study of their thermochemistry and isomerization reaction

  • Luz A. Zapata
  • Steffanía López
  • Pablo RuizEmail author
  • Jairo Quijano
  • Rafael Notario
Original Research


A computational study of the isomerization reaction of a series of halodiazirines to halodiazo compounds (cyclic to open-chain RXCN2 species) has been carried out in order to establish the effect of the substituent groups on the isomerization rates and to obtain computational evidence of reaction mechanisms. Fluorine and chlorine were present as the halogen (X) atom, and the groups R=H, CH3, C2H5, n-C3H7, i-C3H7, cyclo-C3H5, phenyl, OCH3 and OH were used. Thermochemical calculations and natural bond orbital analyses were carried out at the B3LYP/6-31+G(d,p) level of theory. The results allowed us to discuss a reaction mechanism that proceeds in two steps: The first is the extrusion of nitrogen and formation of a carbene through a cyclic transition state that promotes the simultaneous breaking of the two C–N bonds, and the second one is described as the rebounding between the carbene and one of the nitrogen atoms of molecular nitrogen, both formed in the first step. The enthalpies of formation of halodiazirines and halodiazoalkanes have been calculated at the G3 level of theory.


Halodiazirines Diazo compounds Isomerization reaction Substituent effect Transition state 



We thank the financial support of the Universidad Nacional de Colombia-Medellín through the convocatory “Apoyo a grupos de investigación Facultad de Ciencias” under the project number 201010015547.

Supplementary material

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Supplementary material 1 (DOCX 10 kb)
11224_2016_824_MOESM2_ESM.pdf (868 kb)
Supplementary material 2 (PDF 868 kb)


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Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Luz A. Zapata
    • 1
  • Steffanía López
    • 1
  • Pablo Ruiz
    • 1
    Email author
  • Jairo Quijano
    • 1
  • Rafael Notario
    • 2
  1. 1.Laboratorio de Fisicoquímica Orgánica, Facultad de CienciasUniversidad Nacional de Colombia, Sede MedellínMedellínColombia
  2. 2.Instituto de Química Física RocasolanoCSICMadridSpain

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