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  • 1
    ISSN: 0749-1581
    Schlagwort(e): ESR ; Isotropic spectra ; Powder spectra ; Dithiadiazolyl radicals ; Dimerization ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Solution and powder ESR spectra of the 4-trifluoromethyl-1,2,3,5-dithiadiazolyl and 4-pentafluorophenyl-1,2,3,5-dithiadiazolyl free radicals were analysed. Comparison of the ESR parameters with those obtained for the protonated equivalents shows that fluorination produces a drift of unpaired electron spin density away from the nitrogen 2px orbitals towards sulphur 3px orbitals (x is the direction perpendicular to the heterocyclic ring), consistent with an increase in electronegativity of the substituent. The fluorinated radicals dimerize more readily than their protonated counterparts.
    Zusätzliches Material: 4 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 2
    ISSN: 0749-1581
    Schlagwort(e): Electron spin resonance spectroscopy ; Sulphur-nitrogen-containing radicals ; Dithiadiazolyl radicals ; Dithiadiazolyl radicals ; Dithiazophospholyl radicals ; Phosphaalkynes ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Further information has been obtained on the electronic structure of 1,3,2-dithiazol-2-yl radicals. The structure has been well characterized previously except for positions 4 and 5 in the ring. We have obtained solution and powder ESR spectra of radicals substituted with 13C in both positions and of radicals substituted with nitrogen or phosphorus in the 4-position. It is probably the first time that a compound has been prepared containing the ring. Two especially interesting facts emerged from the ESR spectra of these 1,3,2-dithiazolyl radicals: the 13C-substituted radical has a considerable amount of p spin density in the plane of the ring and the phosphorussubstituted radical has a very low unpaired spin density at the phosphorus atom. It is known that 1,3,2,4-dithiadiazolyl radicals isomerize readily by photolysis to the symmetrical 2,3,1,4-dithiadiazolyl radicals; we attempted the same reaction with But and a new radical was produced that we have been unable to identify.
    Zusätzliches Material: 9 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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  • 3
    ISSN: 0749-1581
    Schlagwort(e): ESR ; 1,3,2-Dithiazol-2-yl radicals ; Pyrazine ; Quinoxaline ; Chemistry ; Analytical Chemistry and Spectroscopy
    Quelle: Wiley InterScience Backfile Collection 1832-2000
    Thema: Chemie und Pharmazie
    Notizen: Several symmetrical 1,3,2-dithiazol-2-yl radicals have been examined that have in common nitrogen-containing substituents at the 4- and 5-positions, namely 4,5-dicyano-1,3,2-dithiazol-2-yl, [15N2]-1,3,2-dithiazolo [4,5-b] pyrazin-2-yl and 1,3,2-dithiazoleo [4,5-b] quinoxalin-2-yl. The ESR spectrum of the 4,5-dicyano radical does not reveal any 14N splittings from the cyanide groups; however, the pyrazine and the quinoxaline derivatives do have multi-lined well resolved spectra arising from substantial hyperfine interactions with these nuclei. The interactions are sufficiently large to be observed in the powder spectra of the latter. The presence of proton hyperfine interactions shows that unpaired-electron spin density is delocalized over all the rings. It has been found that the radicals attached to pyrazine and quinoxaline can be incorporated into single crystals of naphthalene and phenazine, respectively.
    Zusätzliches Material: 5 Ill.
    Materialart: Digitale Medien
    Bibliothek Standort Signatur Band/Heft/Jahr Verfügbarkeit
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