New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives
In the present manuscript, we report new insights into the concept of (a)synchronicity in Diels–Alder (DA) reactions in the framework of the reaction force analysis in conjunction with natural population calculations and the atomic resolution of energy derivatives along the intrinsic reaction coordi...
| Main Authors: | , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2022-02-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/27/5/1546 |
| _version_ | 1797474360909365248 |
|---|---|
| author | Bienfait Kabuyaya Isamura Kevin Alan Lobb |
| author_facet | Bienfait Kabuyaya Isamura Kevin Alan Lobb |
| author_sort | Bienfait Kabuyaya Isamura |
| collection | DOAJ |
| description | In the present manuscript, we report new insights into the concept of (a)synchronicity in Diels–Alder (DA) reactions in the framework of the reaction force analysis in conjunction with natural population calculations and the atomic resolution of energy derivatives along the intrinsic reaction coordinate (IRC) path. Our findings suggest that the DA reaction transitions from a preferentially concerted mechanism to a stepwise one in a 0.10 Å window of synchronicity indices ranging from 0.90 to 1.00 Å. We have also shown that the relative position of the global minimum of the reaction force constant with respect to the TS is an alternative and quantifiable indicator of the (a)synchronicity in DA reactions. Moreover, the atomic resolution of energy derivatives reveals that the mechanism of the DA reaction involves two inner elementary processes associated with the formation of each of the two C-C bonds. This resolution goes on to indicate that, in asynchronous reactions, the driving and retarding components of the reaction force are mostly due to the fast and slow-forming C-C bonds (elementary processes) respectively, while in synchronous reactions, both elementary processes retard and drive the process concomitantly and equivalently. |
| first_indexed | 2024-03-09T20:29:54Z |
| format | Article |
| id | doaj.art-361cb5cfae0844d9b6cedc65acab56e5 |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T20:29:54Z |
| publishDate | 2022-02-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-361cb5cfae0844d9b6cedc65acab56e52023-11-23T23:26:03ZengMDPI AGMolecules1420-30492022-02-01275154610.3390/molecules27051546New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy DerivativesBienfait Kabuyaya Isamura0Kevin Alan Lobb1Department of Chemistry, Rhodes University, Makhanda 6140, South AfricaDepartment of Chemistry, Rhodes University, Makhanda 6140, South AfricaIn the present manuscript, we report new insights into the concept of (a)synchronicity in Diels–Alder (DA) reactions in the framework of the reaction force analysis in conjunction with natural population calculations and the atomic resolution of energy derivatives along the intrinsic reaction coordinate (IRC) path. Our findings suggest that the DA reaction transitions from a preferentially concerted mechanism to a stepwise one in a 0.10 Å window of synchronicity indices ranging from 0.90 to 1.00 Å. We have also shown that the relative position of the global minimum of the reaction force constant with respect to the TS is an alternative and quantifiable indicator of the (a)synchronicity in DA reactions. Moreover, the atomic resolution of energy derivatives reveals that the mechanism of the DA reaction involves two inner elementary processes associated with the formation of each of the two C-C bonds. This resolution goes on to indicate that, in asynchronous reactions, the driving and retarding components of the reaction force are mostly due to the fast and slow-forming C-C bonds (elementary processes) respectively, while in synchronous reactions, both elementary processes retard and drive the process concomitantly and equivalently.https://www.mdpi.com/1420-3049/27/5/1546Diels–Alder reactionAMADARreaction force analysisnatural population analysisHellman–Feynman forces |
| spellingShingle | Bienfait Kabuyaya Isamura Kevin Alan Lobb New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives Molecules Diels–Alder reaction AMADAR reaction force analysis natural population analysis Hellman–Feynman forces |
| title | New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives |
| title_full | New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives |
| title_fullStr | New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives |
| title_full_unstemmed | New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives |
| title_short | New Insights into the (A)Synchronicity of Diels–Alder Reactions: A Theoretical Study Based on the Reaction Force Analysis and Atomic Resolution of Energy Derivatives |
| title_sort | new insights into the a synchronicity of diels alder reactions a theoretical study based on the reaction force analysis and atomic resolution of energy derivatives |
| topic | Diels–Alder reaction AMADAR reaction force analysis natural population analysis Hellman–Feynman forces |
| url | https://www.mdpi.com/1420-3049/27/5/1546 |
| work_keys_str_mv | AT bienfaitkabuyayaisamura newinsightsintotheasynchronicityofdielsalderreactionsatheoreticalstudybasedonthereactionforceanalysisandatomicresolutionofenergyderivatives AT kevinalanlobb newinsightsintotheasynchronicityofdielsalderreactionsatheoreticalstudybasedonthereactionforceanalysisandatomicresolutionofenergyderivatives |