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Hydrogen-mediated Stone-Wales isomerization of dicyclopenta[de,mn]anthracene
Sonja Stanković1, Svetlana Marković, Ivan Gutman
1Faculty of Science, University of Kragujevac, 12 Radoja Domanovića, 34000, Kragujevac, Serbia.
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.
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