Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Unveiling the Different Reactivity of Bent and Linear Three-Atom-Components Participating in [3+2] Cycloaddition Reactions

Version 1 : Received: 17 May 2021 / Approved: 18 May 2021 / Online: 18 May 2021 (11:19:57 CEST)

A peer-reviewed article of this Preprint also exists.

Ríos-Gutiérrez, M.; Domingo, L.R.; Ghodsi, F. Unveiling the Different Reactivity of Bent and Linear Three-Atom-Components Participating in [3 + 2] Cycloaddition Reactions. Organics 2021, 2, 274-286. Ríos-Gutiérrez, M.; Domingo, L.R.; Ghodsi, F. Unveiling the Different Reactivity of Bent and Linear Three-Atom-Components Participating in [3 + 2] Cycloaddition Reactions. Organics 2021, 2, 274-286.

Abstract

The 32CA reactions of a series of pairs of bent three-atom-components (B-TACs) and linear TACs (L-TACs) towards electrophilic dicyanoethylene (DCE) have been studied within the Molecular Electron Density Theory in order to understand their different reactivity. ELF analysis indicates that while pseudodiradical B-TACs change their electronic structure to pseudoradical or carbenoid L-TACs upon dehydrogenation, zwitterionic B-TACs experience no remarkable change. Analysis of the CDFT indices indicates that five of the nine studied TACs have a strong nucleophilic character, thus participating in polar reactions towards electrophilic ethylenes. The activation energies of the 32CA reactions of the nine TACs towards electrophilic DCE range from 0.6 to 22.0 kcal·mol-1, which are by between 2.0 and 10.1 kcal·mol-1 lower than those involved in the non-polar 32CA reactions with ethylene. In general, B-TACs are more reactive than their L-TAC counterparts. A change of the regioselectivity is found in these polar 32CA reactions; in general, while B-TACs are meta regioselective, L-TACs are ortho regioselective. Analysis of the geometrical parameters indicates that at all TSs, the formation of the single bond involving the most electrophilic C4 carbon of DCE is more advanced than that involving the C5 one. A change of the asynchronicity in the reactions involving B-TACs and L-TACs is also found.

Keywords

[3+2] cycloaddition reactions; bent and linear three-atom-components; reactivity; regioselectivity; molecular electron density theory

Subject

Chemistry and Materials Science, Analytical Chemistry

Comments (0)

We encourage comments and feedback from a broad range of readers. See criteria for comments and our Diversity statement.

Leave a public comment
Send a private comment to the author(s)
* All users must log in before leaving a comment
Views 0
Downloads 0
Comments 0
Metrics 0


×
Alerts
Notify me about updates to this article or when a peer-reviewed version is published.
We use cookies on our website to ensure you get the best experience.
Read more about our cookies here.