TY - JOUR
T1 - On the Notation of Catastrophes in the Framework of Bonding Evolution Theory
T2 - Case of Normal and Inverse Electron Demand Diels-Alder Reactions
AU - Ayarde-Henríquez, Leandro
AU - Guerra, Cristian
AU - Duque-Noreña, Mario
AU - Rincón, Elizabeth
AU - Pérez, Patricia
AU - Chamorro, Eduardo
N1 - Publisher Copyright:
© 2022 Wiley-VCH GmbH.
PY - 2022
Y1 - 2022
N2 - This paper generalizes very recent and unexpected findings [J. Phys. Chem. A, 2021, 125, 5152–5165] regarding the known “direct- and inverse-electron demand” Diels-Alder mechanisms. Application of bonding evolution theory indicates that the key electron rearrangement associated with significant chemical events (e. g., the breaking/forming processes of bonds) can be characterized via the simplest fold polynomial. For the CC bond formation, neither substituent position nor the type of electronic demand induces a measurable cusp-type signature. As opposed to the case of [4+2] cycloaddition between 1,3-butadiene and ethylene, where the two new CC single bonds occur beyond the transition state (TS) in the activated cases, the first CC bond occurs in the domain of structural stability featuring the TS, whereas the second one remains located in the deactivation path connecting the TS with the cycloadduct.
AB - This paper generalizes very recent and unexpected findings [J. Phys. Chem. A, 2021, 125, 5152–5165] regarding the known “direct- and inverse-electron demand” Diels-Alder mechanisms. Application of bonding evolution theory indicates that the key electron rearrangement associated with significant chemical events (e. g., the breaking/forming processes of bonds) can be characterized via the simplest fold polynomial. For the CC bond formation, neither substituent position nor the type of electronic demand induces a measurable cusp-type signature. As opposed to the case of [4+2] cycloaddition between 1,3-butadiene and ethylene, where the two new CC single bonds occur beyond the transition state (TS) in the activated cases, the first CC bond occurs in the domain of structural stability featuring the TS, whereas the second one remains located in the deactivation path connecting the TS with the cycloadduct.
KW - Bonding evolution theory
KW - Diels-Alder reactions
KW - nonconcerted reaction mechanisms
KW - normal and inverse electron demands
KW - pericyclic reactions
UR - http://www.scopus.com/inward/record.url?scp=85135744188&partnerID=8YFLogxK
U2 - 10.1002/cphc.202200343
DO - 10.1002/cphc.202200343
M3 - Article
AN - SCOPUS:85135744188
SN - 1439-4235
JO - ChemPhysChem
JF - ChemPhysChem
ER -