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 af dette arbejde

30 Citationer (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.

Originalsprog	Engelsk
Tidsskrift	Journal of the American Chemical Society
Vol/bind	103
Udgave nummer	6
Sider (fra-til)	1350-1353
Antal sider	4
ISSN	0002-7863
DOI	https://doi.org/10.1021/ja00396a008
Status	Udgivet - 1 jan. 1981

Adgang til dokumentet

10.1021/ja00396a008

Andre filer og links

Link to publication in Scopus

Citationsformater

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.

I: Journal of the American Chemical Society, Bind 103, Nr. 6, 01.01.1981, s. 1350-1353.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

@article{2f947b5d6bcb44e994290f0d48ed18e2,

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

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.",

author = "Jorgensen, {Flemming S.} and Lars Carlsen and Fritz Duus",

year = "1981",

month = jan,

day = "1",

doi = "10.1021/ja00396a008",

language = "English",

volume = "103",

pages = "1350--1353",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "ACS Publications",

number = "6",

}

TY - JOUR

T1 - The Electronic Structure of β-Thioxoketones. A Photoelectron Spectroscopic Study of the Enol-Enethiol Tautomerism of Thioacetylacetone and Related Compounds

AU - Jorgensen, Flemming S.

AU - Carlsen, Lars

AU - Duus, Fritz

PY - 1981/1/1

Y1 - 1981/1/1

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.

UR - http://www.scopus.com/inward/record.url?scp=0000339679&partnerID=8YFLogxK

U2 - 10.1021/ja00396a008

DO - 10.1021/ja00396a008

M3 - Journal article

AN - SCOPUS:0000339679

SN - 0002-7863

VL - 103

SP - 1350

EP - 1353

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 6

ER -

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

Abstract

Adgang til dokumentet

Andre filer og links

Fingeraftryk

Citationsformater