The Electron Spin Resonance Absorption of the Complexes of Aromatic Sulfur Compounds with Lewis Acids

Kinoshita, Minoru; Akamatu, Hideo

doi:10.1246/bcsj.35.1040

Cited by 19 publications

(3 citation statements)

References 6 publications

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“…Of the remaining spectroscopic tools only electron spin resonance has found application (272,273,343). The best established compound is SbCl6-thianthrene, a colored paramagnetic solid, which has been examined in the solid state and in solution (272,273,343). The unpaired electron that gives rise to the e.s.r.…”

Section: Miscellaneous Spectral Techniquesmentioning

confidence: 99%

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Addition Compounds of Group V Pentahalides

Webster¹

1966

Chem. Rev.

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Section: Miscellaneous Spectral Techniquesmentioning

confidence: 99%

“…spectra of the solids examined (273). The parent organic compounds also yield paramagnetic solutions in concentrated sulfuric acid (228,273,346).…”

Section: Miscellaneous Spectral Techniquesmentioning

confidence: 99%

Addition Compounds of Group V Pentahalides

Webster¹

1966

Chem. Rev.

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“…These sources were Kinoshita in Japan (13,14), Lucken in Switzerland (15), Needier in Minnesota (16) and myself in Texas (9), and each identified the paramagnetic species as the symmetrical cation radical, 3.…”

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Epr and the History of the Thianthrene Cation Radical

Shine¹

1998

Foundations of Modern EPR

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This chapter is concerned with one radical species only, the thianthrene cation radical, Th + . I shall recount the history of the discovery of the structure of Th + not only because it illustrates how EPR was used successfully after initial uncertainties and errors, but also because Th + , with its structure known, was able to play an important role later in studies of reactions of aromatic cation radicals with nucleophiles. I shall not go into those studies, however.The use of EPR spectroscopy to elucidate the structure of aromatic cation radicals began blossoming in the mid-to-late 1950s. It is interesting to note that some of the earliest publications on the subject appeared in the Journal of Chemical Physics, illustrating that the quest to apply EPR to radical structures was still mainly in the hands of physical chemists (1). Perhaps the reason for that was that physical chemists had the ability to build their own spectrometers, or perhaps that organic chemists were not yet acquainted with the powerful tool. It was known then that cation radicals could be formed by treating aromatic compounds with Lewis acids, such as antimony pentachloride, or by dissolving them in concentrated sulfuric acid. Possibly the first to report on EPR and this phenomenon were Hirshon, Gardner and Fraenkel (HGF), who found paramagnetic resonance absorptions with a number of compounds, among which were thiophenol, diphenyl disulfide, and thianthrene (2). It had been shown much earlier by Stenhouse (3) that thiophenol, in forming a purple solution in H2SO4, was oxidized to diphenyl disulfide. This behavior was described in careful detail, subsequently, by Fries and Volk (4), who showed that the diphenyl disulfide was next converted into thianthrene. Fries and Volk deduced that the purple color of solutions of thiophenol and diphenyl disulfide in concentrated H 2 S0 4 was, in fact, caused by the thianthrene, the "magnificent purple" color of whose H 2 S0 4 solution had been already reported by Stenhouse (3). HGF were aware of these early works, and surmised, therefore, that the paramagnetic spectra of the thio compounds in H 2 S0 4 were caused by similar species. The paramagnetic spectra themselves were not given and the report ends with "we are attempting to ascertain what molecular species are responsible for the unusual paramagnetic resonance spectra that are observed in the thio compounds". As far as I am aware, nothing further was reported by HGF, however. Wertz and Vivo were shortly, thereafter, the first to report the characteristic five-line EPR spectrum that was to become so familiar later on (5). Wertz and Vivo obtained the five-line spectrum with solutions of thiophenol, diphenyl disulfide, and thianthrene in H 2 S0 4 . Recognizing that this 202 Foundations of Modern EPR Downloaded from www.worldscientific.com by NANYANG TECHNOLOGICAL UNIVERSITY on 10/02/15. For personal use only.

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Synthesis of poly(arylene sulfide)s by reaction of aromatic sulfides with AlCl₃

Sergeyev¹,

Nedel'kin²

1986

J. Polym. Sci. A Polym. Chem.

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SynopsisMethods have been developed to obtain poly(arylene sulfidek by high-temperature bulk polycondensation of diphenyl sulfide, cyclic aromatic sulfides, a s well as direct reaction of benzene with sulfur, under the action of AICI,,. The reaction proceeds via the formation of colored cation-radical complexes of aromatic sulfides with AICI, and results in polymers of ladder structure with, predominantly, thianthrene units in the chain. Taking linear poly(l,4phenylene sulfide) as an example, AICI, is shown not only to act as a catalyst but also to exert an active influence on the chemical structure of the polymer.

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The Electron Spin Resonance Absorption of the Complexes of Aromatic Sulfur Compounds with Lewis Acids

Cited by 19 publications

References 6 publications

Addition Compounds of Group V Pentahalides

Addition Compounds of Group V Pentahalides

Epr and the History of the Thianthrene Cation Radical

Synthesis of poly(arylene sulfide)s by reaction of aromatic sulfides with AlCl₃

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The Electron Spin Resonance Absorption of the Complexes of Aromatic Sulfur Compounds with Lewis Acids

Cited by 19 publications

References 6 publications

Addition Compounds of Group V Pentahalides

Addition Compounds of Group V Pentahalides

Epr and the History of the Thianthrene Cation Radical

Synthesis of poly(arylene sulfide)s by reaction of aromatic sulfides with AlCl3

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Product

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Synthesis of poly(arylene sulfide)s by reaction of aromatic sulfides with AlCl₃