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

被引：0
作者：
Sonja Stanković
Svetlana Marković
Ivan Gutman
Silva Sretenović
机构：
[1] University of Kragujevac,Faculty of Science
[2] Ghent University,Department of Organic Chemistry, Faculty of Bioscience Engineering
来源：
Journal of Molecular Modeling | 2010年 / 16卷
关键词：
Activation energy lowering; Density functional theory; Electronic structure; Radical mechanism;
D O I：
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中图分类号：
学科分类号：
摘要：
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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页码：1519 / 1527
页数：8
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