Confinement induced thermodynamic and kinetic facilitation of some Diels-Alder reactions inside a CB[7] cavitand
© 2017 Wiley Periodicals, Inc.
| Veröffentlicht in: | Journal of computational chemistry. - 1984. - 39(2018), 3 vom: 30. Jan., Seite 151-160 |
|---|---|
| 1. Verfasser: | |
| Weitere Verfasser: | |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2018
|
| Zugriff auf das übergeordnete Werk: | Journal of computational chemistry |
| Schlagworte: | Journal Article Diels-Alder reaction confinement cucurbit[7]uril rate acceleration supramolecular chemistry |
| Zusammenfassung: | © 2017 Wiley Periodicals, Inc. The effect of geometrical confinement on the Diels-Alder reactions between some model dienes viz. furan, thiophene, cyclopentadiene, benzene, and a classic dienophile, ethylene has been explored by performing density functional theory-based calculations. The effect of confinement has been imposed by a rigid macrocyclic molecule cucurbit[7]uril (CB[7]). Results indicate that all the reactions become thermodynamically more favorable at 298.15 K temperature and one atmospheric pressure inside CB[7] as compared to the corresponding free gaseous state reactions. Moreover, the rate constants associated with the reactions experience manifold enhancement inside CB[7] as compared to the "unconfined" reactions. Suitable contribution from the entropy factor makes the concerned reactions more facile inside CB[7]. The energy gap between the frontier molecular orbitals of the dienes and dienophiles decrease inside CB[7] as compared to that in the free state reactions thereby allowing facile orbital interactions. The nature of interaction as well as bonding has been analyzed with the help of atoms-in-molecules, noncovalent interaction, natural bond orbital as well as energy decomposition analyses. Results suggest that all the guests bind with CB[7] in an attractive fashion. Primarily, noncovalent interactions stabilize the host-guest systems. © 2017 Wiley Periodicals, Inc |
|---|---|
| Beschreibung: | Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.25094 |