Synthesis, Structural Elucidation, Cyclic Voltammetry, and Theoretical Modelling of 2-Ferrocenyl-4H-benzo[e][1,3]thiazines and 2-Aryl-4H-ferroceno[e][1,3]thiazines

Kinga Judit Fodor, Kristóf Hegedüs, Péter Csomós, L. Fodor, Dorottya Gubán, Pál Sohár, Antal Csámpai

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

2-Ferrocenyl-4H-benzo[e][1,3]thiazine and its 6,7-dimethoxy derivative were prepared by a Bischler–Napieralski-type annulation of the Mannich adducts of ferrocenecarboxamide, formaldehyde, and the corresponding thiophenol. A more efficient synthetic pathway, comprising a directed lithiation/iodination sequence followed by standard functional-group transformations and a final copper-catalyzed cyclization, was elaborated to convert [(dimethylamino)methyl]ferrocene into racemic mixtures of the first representatives of planar-chiral 4H-ferroceno[e][1,3]thiazines. A similar strategy with 2-iodobenzyl bromide as the precursor enabled a highly improved synthesis of 2-ferrocenyl-4H-benzo[e][1,3]thiazine. The relative tendency of the new ferrocene-based thiazines, composed of potential redox sites assembled in different molecular architectures, to behave as donors in single-electron transfer (SET) reactions was studied by cyclic voltammetry (CV) and DFT calculations. The results disclosed that 2-ferrocenyl-4H-ferroceno[e][1,3]thiazine can undergo two consecutive redox steps and is the most efficient reductant among the prepared models; it has the lowest first half-cell potential, the highest-energy highest occupied molecular orbital (HOMO) concentrated on the fused metallocene unit and the lowest first ionization energy.

Original languageEnglish
Pages (from-to)511-520
Number of pages10
JournalEuropean Journal of Inorganic Chemistry
Volume2017
Issue number2
DOIs
Publication statusPublished - 2017

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Thiazines
Cyclic voltammetry
Ionization potential
Cyclization
Reducing Agents
Molecular orbitals
Bromides
Discrete Fourier transforms
Functional groups
Formaldehyde
Copper
Derivatives
Electrons

Keywords

  • Cyclic voltammetry
  • Cyclization
  • Electronic structure
  • Metallocenes
  • Molecular modeling

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Synthesis, Structural Elucidation, Cyclic Voltammetry, and Theoretical Modelling of 2-Ferrocenyl-4H-benzo[e][1,3]thiazines and 2-Aryl-4H-ferroceno[e][1,3]thiazines. / Fodor, Kinga Judit; Hegedüs, Kristóf; Csomós, Péter; Fodor, L.; Gubán, Dorottya; Sohár, Pál; Csámpai, Antal.

In: European Journal of Inorganic Chemistry, Vol. 2017, No. 2, 2017, p. 511-520.

Research output: Contribution to journalArticle

Fodor, Kinga Judit ; Hegedüs, Kristóf ; Csomós, Péter ; Fodor, L. ; Gubán, Dorottya ; Sohár, Pál ; Csámpai, Antal. / Synthesis, Structural Elucidation, Cyclic Voltammetry, and Theoretical Modelling of 2-Ferrocenyl-4H-benzo[e][1,3]thiazines and 2-Aryl-4H-ferroceno[e][1,3]thiazines. In: European Journal of Inorganic Chemistry. 2017 ; Vol. 2017, No. 2. pp. 511-520.
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AU - Fodor, Kinga Judit

AU - Hegedüs, Kristóf

AU - Csomós, Péter

AU - Fodor, L.

AU - Gubán, Dorottya

AU - Sohár, Pál

AU - Csámpai, Antal

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N2 - 2-Ferrocenyl-4H-benzo[e][1,3]thiazine and its 6,7-dimethoxy derivative were prepared by a Bischler–Napieralski-type annulation of the Mannich adducts of ferrocenecarboxamide, formaldehyde, and the corresponding thiophenol. A more efficient synthetic pathway, comprising a directed lithiation/iodination sequence followed by standard functional-group transformations and a final copper-catalyzed cyclization, was elaborated to convert [(dimethylamino)methyl]ferrocene into racemic mixtures of the first representatives of planar-chiral 4H-ferroceno[e][1,3]thiazines. A similar strategy with 2-iodobenzyl bromide as the precursor enabled a highly improved synthesis of 2-ferrocenyl-4H-benzo[e][1,3]thiazine. The relative tendency of the new ferrocene-based thiazines, composed of potential redox sites assembled in different molecular architectures, to behave as donors in single-electron transfer (SET) reactions was studied by cyclic voltammetry (CV) and DFT calculations. The results disclosed that 2-ferrocenyl-4H-ferroceno[e][1,3]thiazine can undergo two consecutive redox steps and is the most efficient reductant among the prepared models; it has the lowest first half-cell potential, the highest-energy highest occupied molecular orbital (HOMO) concentrated on the fused metallocene unit and the lowest first ionization energy.

AB - 2-Ferrocenyl-4H-benzo[e][1,3]thiazine and its 6,7-dimethoxy derivative were prepared by a Bischler–Napieralski-type annulation of the Mannich adducts of ferrocenecarboxamide, formaldehyde, and the corresponding thiophenol. A more efficient synthetic pathway, comprising a directed lithiation/iodination sequence followed by standard functional-group transformations and a final copper-catalyzed cyclization, was elaborated to convert [(dimethylamino)methyl]ferrocene into racemic mixtures of the first representatives of planar-chiral 4H-ferroceno[e][1,3]thiazines. A similar strategy with 2-iodobenzyl bromide as the precursor enabled a highly improved synthesis of 2-ferrocenyl-4H-benzo[e][1,3]thiazine. The relative tendency of the new ferrocene-based thiazines, composed of potential redox sites assembled in different molecular architectures, to behave as donors in single-electron transfer (SET) reactions was studied by cyclic voltammetry (CV) and DFT calculations. The results disclosed that 2-ferrocenyl-4H-ferroceno[e][1,3]thiazine can undergo two consecutive redox steps and is the most efficient reductant among the prepared models; it has the lowest first half-cell potential, the highest-energy highest occupied molecular orbital (HOMO) concentrated on the fused metallocene unit and the lowest first ionization energy.

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KW - Cyclization

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