The Electronic Structure of β-Thioxoketones. A Photoelectron Spectroscopic Study of the Enol-Enethiol Tautomerism of Thioacetylacetone and Related Compounds

Flemming S. Jorgensen; Lars Carlsen; Fritz Duus

doi:10.1021/ja00396a008

The Electronic Structure of β-Thioxoketones. A Photoelectron Spectroscopic Study of the Enol-Enethiol Tautomerism of Thioacetylacetone and Related Compounds

Flemming S. Jorgensen^*, Lars Carlsen, Fritz Duus

^*Corresponding author for this work

30 Citations (Scopus)

Abstract

The He I photoelectron spectra of thioacetylacetone, 2-acetylcyclohexanethione, 2-thioacetylcyclohexanone, and the S-methyl derivative of thioacetylacetone has been recorded and interpreted by comparison with PE data on related compounds. The interpretation has been supported by semiempirical molecular orbital calculations based on the CNDO/B, CNDO/S, and MNDO methods on the enol and enethiol forms of monothiomalondialdehyde. The three lowest ionization energies were determined as ns ͌π₃<π₂ for the enol form and as π₃ πn₀ <π₂ for the enethiol form. The influence of hydrogen bonding on the electronic structure is discussed. Attention is called to the possibility of distinguishing generally by means of PE spectroscopy between the enol and enethiol forms of a tautomeric equilibrium system under consideration.

Original language	English
Journal	Journal of the American Chemical Society
Volume	103
Issue number	6
Pages (from-to)	1350-1353
Number of pages	4
ISSN	0002-7863
DOIs	https://doi.org/10.1021/ja00396a008
Publication status	Published - 1 Jan 1981

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The Electronic Structure of β-Thioxoketones. A Photoelectron Spectroscopic Study of the Enol-Enethiol Tautomerism of Thioacetylacetone and Related Compounds. / Jorgensen, Flemming S.; Carlsen, Lars; Duus, Fritz.

In: Journal of the American Chemical Society, Vol. 103, No. 6, 01.01.1981, p. 1350-1353.

Research output: Contribution to journal › Journal article › Research › peer-review

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abstract = "The He I photoelectron spectra of thioacetylacetone, 2-acetylcyclohexanethione, 2-thioacetylcyclohexanone, and the S-methyl derivative of thioacetylacetone has been recorded and interpreted by comparison with PE data on related compounds. The interpretation has been supported by semiempirical molecular orbital calculations based on the CNDO/B, CNDO/S, and MNDO methods on the enol and enethiol forms of monothiomalondialdehyde. The three lowest ionization energies were determined as ns ͌π3<π2 for the enol form and as π3 πn0 <π2 for the enethiol form. The influence of hydrogen bonding on the electronic structure is discussed. Attention is called to the possibility of distinguishing generally by means of PE spectroscopy between the enol and enethiol forms of a tautomeric equilibrium system under consideration.",

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AU - Duus, Fritz

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N2 - The He I photoelectron spectra of thioacetylacetone, 2-acetylcyclohexanethione, 2-thioacetylcyclohexanone, and the S-methyl derivative of thioacetylacetone has been recorded and interpreted by comparison with PE data on related compounds. The interpretation has been supported by semiempirical molecular orbital calculations based on the CNDO/B, CNDO/S, and MNDO methods on the enol and enethiol forms of monothiomalondialdehyde. The three lowest ionization energies were determined as ns ͌π3<π2 for the enol form and as π3 πn0 <π2 for the enethiol form. The influence of hydrogen bonding on the electronic structure is discussed. Attention is called to the possibility of distinguishing generally by means of PE spectroscopy between the enol and enethiol forms of a tautomeric equilibrium system under consideration.

AB - The He I photoelectron spectra of thioacetylacetone, 2-acetylcyclohexanethione, 2-thioacetylcyclohexanone, and the S-methyl derivative of thioacetylacetone has been recorded and interpreted by comparison with PE data on related compounds. The interpretation has been supported by semiempirical molecular orbital calculations based on the CNDO/B, CNDO/S, and MNDO methods on the enol and enethiol forms of monothiomalondialdehyde. The three lowest ionization energies were determined as ns ͌π3<π2 for the enol form and as π3 πn0 <π2 for the enethiol form. The influence of hydrogen bonding on the electronic structure is discussed. Attention is called to the possibility of distinguishing generally by means of PE spectroscopy between the enol and enethiol forms of a tautomeric equilibrium system under consideration.

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The Electronic Structure of β-Thioxoketones. A Photoelectron Spectroscopic Study of the Enol-Enethiol Tautomerism of Thioacetylacetone and Related Compounds

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