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Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation of Cyclo[18]carbon–Piperidine
[Image: see text] Recent quantum chemical computations demonstrated the electron-acceptance behavior of this highly reactive cyclo[18]carbon (C(18)) ring with piperidine (pip). The C(18)–pip complexation exhibited a double-well potential along the N–C reaction coordinate, forming a van der Waals (vd...
Autores principales: | , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2022
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8900127/ https://www.ncbi.nlm.nih.gov/pubmed/35180344 http://dx.doi.org/10.1021/acs.jpcb.2c00218 |
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author | Nandi, Ashim Martin, Jan M. L. |
author_facet | Nandi, Ashim Martin, Jan M. L. |
author_sort | Nandi, Ashim |
collection | PubMed |
description | [Image: see text] Recent quantum chemical computations demonstrated the electron-acceptance behavior of this highly reactive cyclo[18]carbon (C(18)) ring with piperidine (pip). The C(18)–pip complexation exhibited a double-well potential along the N–C reaction coordinate, forming a van der Waals (vdW) adduct and a more stable, strong covalent/dative bond (DB) complex by overcoming a low activation barrier. By means of direct dynamical computations using canonical variational transition state theory (CVT), including the small-curvature tunneling (SCT), we show the conspicuous role of heavy atom quantum mechanical tunneling (QMT) in the transformation of vdW to DB complex in the solvent phase near absolute zero. Below 50 K, the reaction is entirely driven by QMT, while at 30 K, the QMT rate is too rapid (k(T) ∼ 0.02 s(–1)), corresponding to a half-life time of 38 s, indicating that the vdW adduct will have a fleeting existence. We also explored the QMT rates of other cyclo[n]carbon–pip systems. This study sheds light on the decisive role of QMT in the covalent/DB formation of the C(18)–pip complex at cryogenic temperatures. |
format | Online Article Text |
id | pubmed-8900127 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-89001272022-03-08 Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation of Cyclo[18]carbon–Piperidine Nandi, Ashim Martin, Jan M. L. J Phys Chem B [Image: see text] Recent quantum chemical computations demonstrated the electron-acceptance behavior of this highly reactive cyclo[18]carbon (C(18)) ring with piperidine (pip). The C(18)–pip complexation exhibited a double-well potential along the N–C reaction coordinate, forming a van der Waals (vdW) adduct and a more stable, strong covalent/dative bond (DB) complex by overcoming a low activation barrier. By means of direct dynamical computations using canonical variational transition state theory (CVT), including the small-curvature tunneling (SCT), we show the conspicuous role of heavy atom quantum mechanical tunneling (QMT) in the transformation of vdW to DB complex in the solvent phase near absolute zero. Below 50 K, the reaction is entirely driven by QMT, while at 30 K, the QMT rate is too rapid (k(T) ∼ 0.02 s(–1)), corresponding to a half-life time of 38 s, indicating that the vdW adduct will have a fleeting existence. We also explored the QMT rates of other cyclo[n]carbon–pip systems. This study sheds light on the decisive role of QMT in the covalent/DB formation of the C(18)–pip complex at cryogenic temperatures. American Chemical Society 2022-02-18 2022-03-03 /pmc/articles/PMC8900127/ /pubmed/35180344 http://dx.doi.org/10.1021/acs.jpcb.2c00218 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Nandi, Ashim Martin, Jan M. L. Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation of Cyclo[18]carbon–Piperidine |
title | Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation
of Cyclo[18]carbon–Piperidine |
title_full | Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation
of Cyclo[18]carbon–Piperidine |
title_fullStr | Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation
of Cyclo[18]carbon–Piperidine |
title_full_unstemmed | Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation
of Cyclo[18]carbon–Piperidine |
title_short | Heavy-Atom Tunneling in the Covalent/Dative Bond Complexation
of Cyclo[18]carbon–Piperidine |
title_sort | heavy-atom tunneling in the covalent/dative bond complexation
of cyclo[18]carbon–piperidine |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8900127/ https://www.ncbi.nlm.nih.gov/pubmed/35180344 http://dx.doi.org/10.1021/acs.jpcb.2c00218 |
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