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Journal of Molecular Modeling

, Volume 16, Issue 9, pp 1519–1527 | Cite as

Hydrogen-mediated Stone-Wales isomerization of dicyclopenta[de,mn]anthracene

  • Sonja Stanković
  • Svetlana MarkovićEmail author
  • Ivan Gutman
  • Silva Sretenović
Original Paper

Abstract

The mechanism of transformation of two radicals (R1p and R1i) obtained by addition of a hydrogen atom to an external and internal carbon atom of dicyclopenta[de,mn]anthracene (P1) was investigated. Two pathways were revealed. The first mechanism is a one-step process, whereas the second mechanism includes two transition states and a cyclobutyl intermediate. The formation of R1p and R1i and the homolytic cleavage of the radicals obtained during the isomerization processes were also examined. In both pathways the addition of a hydrogen atom to the internal carbon significantly lowers the activation energy for hydrogen-mediated isomerization of P1 to acefluoranthene. This finding could be explained by the specific electronic structures of the transition states and intermediates participating in the isomerization processes.

Figure

Addition of hydrogen atom to an internal carbon lowers the activation barrier for the Stone-Wales rearrangement

Keywords

Activation energy lowering Density functional theory Electronic structure Radical mechanism 

Notes

Acknowledgments

This work is supported by the Ministry of science of Serbia, projects No 144015G and 142025.

Supplementary material

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894_2010_669_MOESM2_ESM.doc (94 kb)
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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Sonja Stanković
    • 1
    • 2
  • Svetlana Marković
    • 1
    Email author
  • Ivan Gutman
    • 1
  • Silva Sretenović
    • 1
  1. 1.Faculty of ScienceUniversity of KragujevacKragujevacSerbia
  2. 2.Department of Organic Chemistry, Faculty of Bioscience EngineeringGhent UniversityGhentBelgium

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