Computational Study of the Reactions of Chlorine Radicals with Atmospheric
Organic Compounds Featuring NHx–π-Bond
(x = 1, 2) Structures
Version 2 2017-02-20, 12:49
Version 1 2017-02-15, 17:05
Posted on 2017-02-20 - 12:49
Among
160 organic NHx-containing compounds (x = 1, 2) detected in the atmosphere, there are about 80
species for which the molecules contain p−π conjugate
substructures of NHx–π-bonds.
Here, chlorine radical (·Cl)-initiated reactions for formamide, N-methylformamide, ethenamine, and aniline, as their cases,
were investigated by a quantum chemical method [CCSD(T)/aug-cc-pVTZ//MP2/6-31+G(3df,2p)]
and kinetics modeling. The calculated overall rate constants are 5.5
× 10–11, 2.3 × 10–10, 2.7 × 10–10, and 1.7 × 10–10 cm3 molecule–1 s–1 for formamide, N-methylformamide, ethenamine, and
aniline, respectively, and agree well with experimental values for
available ones. Importantly, the results show that the reactions of
two amides with ·Cl mainly lead to C-center radicals via ·Cl
abstracting the −CHO hydrogen of amides. However, both ethenamine
+ ·Cl and aniline + ·Cl reactions mainly produce delocalized
radicals with the radical center on the C-site and N-site via a ·Cl
addition and the −NHx hydrogen
abstraction pathway, respectively. Therefore, this study reveals that
reactions of organic NHx-containing compounds
with ·Cl have various reaction mechanisms, in contrast to our
previous understanding that −NHx hydrogen abstraction pathways, leading to N-center radicals, are
the most favorable. The unveiled reaction mechanisms should be of
significance for the risk assessment of atmospheric organic NHx-containing compounds and enriching ·Cl
chemistry.
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Xie, Hong-Bin; Ma, Fangfang; Yu, Qi; He, Ning; Chen, Jingwen (2017). Computational Study of the Reactions of Chlorine Radicals with Atmospheric
Organic Compounds Featuring NHx–π-Bond
(x = 1, 2) Structures. ACS Publications. Collection. https://doi.org/10.1021/acs.jpca.6b11418
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AUTHORS (5)
HX
Hong-Bin Xie
FM
Fangfang Ma
QY
Qi Yu
NH
Ning He
JC
Jingwen Chen