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Indene Formation under Single‐Collision Conditions from the Reaction of Phenyl Radicals with Allene and Methylacetylene—A Crossed Molecular Beam and Ab Initio Study
Author(s) -
Parker Dr Dorian S. N.,
Zhang Dr Fangtong,
Kaiser Dr Ralf I.,
Kislov Dr Vadim V.,
Mebel Dr Alexander M.
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100535
Subject(s) - allene , indene , crossed molecular beam , radical , chemistry , deuterium , photochemistry , ab initio , computational chemistry , organic chemistry , molecule , atomic physics , catalysis , physics
Polycyclic aromatic hydrocarbons (PAHs) are regarded as key intermediates in the molecular growth process that forms soot from incomplete fossil fuel combustion. Although heavily researched, the reaction mechanisms for PAH formation have only been investigated through bulk experiments; therefore, current models remain conjectural. We report the first observation of a directed synthesis of a PAH under single‐collision conditions. By using a crossed‐molecular‐beam apparatus, phenyl radicals react with C 3 H 4 isomers, methylacetylene and allene, to form indene at collision energies of 45 kJ mol −1 . The reaction dynamics supported by theoretical calculations show that both isomers decay through the same collision complex, are indirect, have long lifetimes, and form indene in high yields. Through the use of deuterium‐substituted reactants, we were able to identify the reaction pathway to indene.