Mechanism(s) of thermal decomposition of N-Nitrosoamides: A density functional theory study
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Mechanism(s) of thermal decomposition of N-Nitrosoamides : A density functional theory study. / Brea, Oriana; Daver, Henrik; Rebek, Julius; Himo, Fahmi.
In: Tetrahedron, Vol. 75, No. 8, 22.02.2019, p. 929-935.Research output: Contribution to journal › Journal article › Research › peer-review
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TY - JOUR
T1 - Mechanism(s) of thermal decomposition of N-Nitrosoamides
T2 - A density functional theory study
AU - Brea, Oriana
AU - Daver, Henrik
AU - Rebek, Julius
AU - Himo, Fahmi
PY - 2019/2/22
Y1 - 2019/2/22
N2 - The thermal decomposition of N-nitrosoamides has experimentally been demonstrated to depend on several factors, such as temperature, solvent and the substituents on the substrate. Consequently, a number of reaction mechanisms have been proposed for this process in the literature. In this work, we present a comprehensive computational investigation in which we examine the detailed reaction mechanisms for two N-nitrosoamides (with aliphatic and aromatic substituents) in two different solvents (mesitylene and methanol). It is shown that the reaction mechanism can change dramatically with the nature of the substrate and the choice of solvent. Importantly, it is found that the polar solvent stabilizes ion-pairs that are unstable in the non-polar solvent, which can play a key role in the mechanism.
AB - The thermal decomposition of N-nitrosoamides has experimentally been demonstrated to depend on several factors, such as temperature, solvent and the substituents on the substrate. Consequently, a number of reaction mechanisms have been proposed for this process in the literature. In this work, we present a comprehensive computational investigation in which we examine the detailed reaction mechanisms for two N-nitrosoamides (with aliphatic and aromatic substituents) in two different solvents (mesitylene and methanol). It is shown that the reaction mechanism can change dramatically with the nature of the substrate and the choice of solvent. Importantly, it is found that the polar solvent stabilizes ion-pairs that are unstable in the non-polar solvent, which can play a key role in the mechanism.
KW - Computational chemistry
KW - Density functional theory
KW - Nitrosoamides
KW - Reaction mechanism
KW - Transition state
UR - http://www.scopus.com/inward/record.url?scp=85060083379&partnerID=8YFLogxK
U2 - 10.1016/j.tet.2018.12.054
DO - 10.1016/j.tet.2018.12.054
M3 - Journal article
AN - SCOPUS:85060083379
VL - 75
SP - 929
EP - 935
JO - Tetrahedron
JF - Tetrahedron
SN - 0040-4020
IS - 8
ER -
ID: 241045162