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Updated: Jul 19, 2026

Preparation of a Corannulene-functionalized Hexahelicene by Copper(I)-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
Published on: September 18, 2016
Radical-molecule reactions for aromatic growth: a case study for cyclopentadienyl and acenaphthylene
1Department of Mechanical Engineering, University of Michigan, Ann Arbor, Michigan 48104, USA.
Abstract:
Polycyclic aromatic hydrocarbon growth from acenaphthylene and cyclopentadienyl was investigated by using the B3LYP/6-31G(d,p) and BH&HLYP/6-31G(d,p) levels of theory as well as transition state theory. The reaction pathways of cyclopentadienyl bearing hydrocarbons are different from those without these moieties and cannot be adequately accounted for by the existing acetylene addition and aryl-aryl addition mechanisms. The reaction mechanisms identified in this paper lead to the formation of fluoranthene, aceanthrylene, and acephenanthrylene. Rate constants of the radical-molecule addition and subsequent intramolecular addition steps predict that the 1,2 double bond in acenaphthylene is much more reactive than the 3,4 and 4,5 double bonds. Fluoranthene is the most abundant product produced at high temperatures and the yield of acephenanthrylene is bigger than that of aceanthrylene. The computational results are discussed in light of pyrolysis experiments on CPD-indene and CPD-acenaphthylene mixtures conducted by Prof. Mulholland's research group reported in a previous work.
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