Dokument: Hydrogen Activation by a σσ*-Carbene Through Quantum Tunneling
| Titel: | Hydrogen Activation by a σσ*-Carbene Through Quantum Tunneling | |||||||
| URL für Lesezeichen: | https://docserv.uni-duesseldorf.de/servlets/DocumentServlet?id=72816 | |||||||
| URN (NBN): | urn:nbn:de:hbz:061-20260402-111046-8 | |||||||
| Kollektion: | Publikationen | |||||||
| Sprache: | Englisch | |||||||
| Dokumententyp: | Wissenschaftliche Texte » Artikel, Aufsatz | |||||||
| Medientyp: | Text | |||||||
| Autoren: | Meisner, Jan [Autor] Bhagat, Virinder [Autor] Wagner, J. Philipp [Autor] | |||||||
| Dateien: |
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| Beschreibung: | The electronic structure of carbenes arises from the occupation of a σ and a π frontier orbital. While parent methylene possesses a triplet ground state (σ1π1), substituents are capable of stabilizing the singlet as the ground state (σ2π0 or σ0π2) by altering the frontier orbital energies. Here, we reveal that the 1,2[I]-shift isomer of 2-iodopyridine, the N-iodo Hammick intermediate, features a resonance between its carbene σ and N–I bond σ* orbitals, rendering them frontier orbitals. This singlet carbene is efficiently generated via UV photolysis of 2-iodopyridine in solid neon at 4.4 K and reacts with molecular hydrogen – but not deuterium – via N–I bond cleavage enabled by quantum tunneling. Instanton theory computations demonstrate the preference for a concerted hydrogen addition mechanism at elevated temperatures, while hydrogen atom abstraction dominates below 100 K despite a higher kinetic barrier for this process. Our findings introduce an unprecedented carbene class, unlocking new opportunities for reactivity and electronic structure explorations. | |||||||
| Rechtliche Vermerke: | Originalveröffentlichung:
Bhagat, V., Meisner, J., & Wagner, J. P. (2025). Hydrogen Activation by a σσ*-Carbene Through Quantum Tunneling. Journal of the American Chemical Society, 147(39), 35275–35282. https://doi.org/10.1021/jacs.5c06016 | |||||||
| Lizenz: |  Dieses Werk ist lizenziert unter einer Creative Commons Namensnennung 4.0 International Lizenz | |||||||
| Fachbereich / Einrichtung: | Mathematisch- Naturwissenschaftliche Fakultät | |||||||
| Dokument erstellt am: | 02.04.2026 | |||||||
| Dateien geändert am: | 02.04.2026 |
