title: Hydrogen-mediated Stone-Wales isomerization of dicyclopenta[de,mn]anthracene.
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.
authors.affiliation: Faculty of Science, University of Kragujevac, 12 Radoja Domanovića, 34000, Kragujevac, Serbia.
authors.forename: Sonja
authors.initials: S
authors.lastname: Stanković
authors.forename: Svetlana
authors.initials: S
authors.lastname: Marković
authors.forename: Ivan
authors.initials: I
authors.lastname: Gutman
authors.forename: Silva
authors.initials: S
authors.lastname: Sretenović
mesh_terms: D000873:Anthracenes / Q000737:chemistry*; D003517:Cyclopentanes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007536:Isomerism; D008958:Models, Molecular; D013816:Thermodynamics
chemical_list: D000873:Anthracenes; D003517:Cyclopentanes; C544297:dicyclopenta(de,mn)anthracene; D006859:Hydrogen