Quantum chemical investigations of the thermal and photoinduced proton-transfer reactions of 2-(2′,4′-dinitrobenzyl)pyridine

Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review

Autoren

  • Irmgard Frank
  • Stefan Grimme
  • Sigrid D. Peyerimhoff

Externe Organisationen

  • Rheinische Friedrich-Wilhelms-Universität Bonn
  • Max-Planck-Institut für Festkörperforschung
Forschungs-netzwerk anzeigen

Details

OriginalspracheEnglisch
Seiten (von - bis)16187-16194
Seitenumfang8
FachzeitschriftJournal of Physical Chemistry
Jahrgang100
Ausgabenummer40
PublikationsstatusVeröffentlicht - 3 Okt. 1996
Extern publiziertJa

Abstract

Quantum chemical calculations of the proton-transfer system 2-(2′,4′-dinitrobenzyl)pyridine (DNBP) and of derivatives with larger aromatic bases are presented. These systems undergo photochemical isomerizations from a stable form to two different photoisomers. Ab initio methods are employed to investigate the isomerization of methylimine to vinylamine as a model system for the proton-transfer reaction of DNBP. The ground and excited states of both isomers and of the transition state for the isomerization are studied with Hartree-Fock and MRD-CI (multireference singles and doubles CI) methods. The isomerizations of the larger system DNBP and its derivatives are investigated with semiempirical PM3-SCF and PM3-MRD-CI methods. The intrinsic reaction coordinate formalism is used for calculating the reaction pathways from the optimized transition states. The relative stabilities of the various isomers and the mechanism of the intramolecular proton-transfer reaction are discussed. The ortho-nitro group assists the proton transfer from the methylene group to the pyridine ring. The experimentally observed reaction barriers are reproduced by taking crystal effects into account.

ASJC Scopus Sachgebiete

Zitieren

Quantum chemical investigations of the thermal and photoinduced proton-transfer reactions of 2-(2′,4′-dinitrobenzyl)pyridine. / Frank, Irmgard; Grimme, Stefan; Peyerimhoff, Sigrid D.
in: Journal of Physical Chemistry, Jahrgang 100, Nr. 40, 03.10.1996, S. 16187-16194.

Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review

Frank, I, Grimme, S & Peyerimhoff, SD 1996, 'Quantum chemical investigations of the thermal and photoinduced proton-transfer reactions of 2-(2′,4′-dinitrobenzyl)pyridine', Journal of Physical Chemistry, Jg. 100, Nr. 40, S. 16187-16194. https://doi.org/10.1021/jp960923+
Frank, I., Grimme, S., & Peyerimhoff, S. D. (1996). Quantum chemical investigations of the thermal and photoinduced proton-transfer reactions of 2-(2′,4′-dinitrobenzyl)pyridine. Journal of Physical Chemistry, 100(40), 16187-16194. https://doi.org/10.1021/jp960923+
Frank I, Grimme S, Peyerimhoff SD. Quantum chemical investigations of the thermal and photoinduced proton-transfer reactions of 2-(2′,4′-dinitrobenzyl)pyridine. Journal of Physical Chemistry. 1996 Okt 3;100(40):16187-16194. doi: 10.1021/jp960923+
Frank, Irmgard ; Grimme, Stefan ; Peyerimhoff, Sigrid D. / Quantum chemical investigations of the thermal and photoinduced proton-transfer reactions of 2-(2′,4′-dinitrobenzyl)pyridine. in: Journal of Physical Chemistry. 1996 ; Jahrgang 100, Nr. 40. S. 16187-16194.
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AU - Grimme, Stefan

AU - Peyerimhoff, Sigrid D.

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N2 - Quantum chemical calculations of the proton-transfer system 2-(2′,4′-dinitrobenzyl)pyridine (DNBP) and of derivatives with larger aromatic bases are presented. These systems undergo photochemical isomerizations from a stable form to two different photoisomers. Ab initio methods are employed to investigate the isomerization of methylimine to vinylamine as a model system for the proton-transfer reaction of DNBP. The ground and excited states of both isomers and of the transition state for the isomerization are studied with Hartree-Fock and MRD-CI (multireference singles and doubles CI) methods. The isomerizations of the larger system DNBP and its derivatives are investigated with semiempirical PM3-SCF and PM3-MRD-CI methods. The intrinsic reaction coordinate formalism is used for calculating the reaction pathways from the optimized transition states. The relative stabilities of the various isomers and the mechanism of the intramolecular proton-transfer reaction are discussed. The ortho-nitro group assists the proton transfer from the methylene group to the pyridine ring. The experimentally observed reaction barriers are reproduced by taking crystal effects into account.

AB - Quantum chemical calculations of the proton-transfer system 2-(2′,4′-dinitrobenzyl)pyridine (DNBP) and of derivatives with larger aromatic bases are presented. These systems undergo photochemical isomerizations from a stable form to two different photoisomers. Ab initio methods are employed to investigate the isomerization of methylimine to vinylamine as a model system for the proton-transfer reaction of DNBP. The ground and excited states of both isomers and of the transition state for the isomerization are studied with Hartree-Fock and MRD-CI (multireference singles and doubles CI) methods. The isomerizations of the larger system DNBP and its derivatives are investigated with semiempirical PM3-SCF and PM3-MRD-CI methods. The intrinsic reaction coordinate formalism is used for calculating the reaction pathways from the optimized transition states. The relative stabilities of the various isomers and the mechanism of the intramolecular proton-transfer reaction are discussed. The ortho-nitro group assists the proton transfer from the methylene group to the pyridine ring. The experimentally observed reaction barriers are reproduced by taking crystal effects into account.

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