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@ARTICLE{Vereecken:902289,
author = {Vereecken, L. and Vu, G. and Wahner, A. and
Kiendler-Scharr, A. and Nguyen, H. M. T.},
title = {{A} structure activity relationship for ring closure
reactions in unsaturated alkylperoxy radicals},
journal = {Physical chemistry, chemical physics},
volume = {23},
number = {31},
issn = {1463-9084},
address = {Cambridge},
publisher = {RSC Publ.},
reportid = {FZJ-2021-04152},
pages = {16564 - 16576},
year = {2021},
abstract = {Terpenoids are an important class of multi-unsaturated
volatile organic compounds emitted to the atmosphere. During
their oxidation in the troposphere, unsaturated peroxy
radicals are formed, which may undergo ring closure
reactions by an addition of the radical oxygen atom on
either of the carbons in the C[double bond, length as
m-dash]C double bond. This study describes a quantum
chemical and theoretical kinetic study of the rate of ring
closure, finding that the reactions are comparatively fast
with rates often exceeding 1 s−1 at room temperature,
making these reactions competitive in low-NOx environments
and allowing for continued autoxidation by ring closure. A
structure–activity relationship (SAR) is presented for 5-
to 8-membered ring closure in unsaturated RO2 radicals with
aliphatic substituents, with some analysis of the impact of
oxygenated substituents. H-migration in the cycloperoxide
peroxy radicals formed after the ring closure was found to
be comparatively slow for unsubstituted RO2 radicals. In the
related cycloperoxide alkoxy radicals, migration of H-atoms
implanted on the ring was similarly found to be slower than
for non-cyclic alkoxy radicals and is typically not
competitive against decomposition reactions that lead to
cycloperoxide ring breaking. Ring closure reactions may
constitute an important reaction channel in the atmospheric
oxidation of terpenoids and could promote continued
autoxidation, though the impact is likely to be strongly
dependent on the specific molecular backbone.},
cin = {IEK-8},
ddc = {540},
cid = {I:(DE-Juel1)IEK-8-20101013},
pnm = {2111 - Air Quality (POF4-211)},
pid = {G:(DE-HGF)POF4-2111},
typ = {PUB:(DE-HGF)16},
pubmed = {34313271},
UT = {WOS:000677750300001},
doi = {10.1039/D1CP02758A},
url = {https://juser.fz-juelich.de/record/902289},
}