The preparation and isolation of 5-methyl-1,3,2,4-dithiadiazolyl and the facile rearrangement of the 1,3,2,4-dithiadiazolyl radicals to the disulphide isomers, 2,3,1,4-dithiadiazolyl

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Section: Introductionmentioning

confidence: 99%

The preparation and X-ray crystal structure of Te(N₃)₃SbF₆ containing the triazidotellurium(IV) cation, Te(N₃)₃⁺

Johnson¹,

MacLean²,

Passmore³

et al. 1989

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“…to RCNSSN. was previously studied for some alkyl derivatives (6,7). In this work, we determined the relative rates of this rearrangement for some related aryl derivatives and found that the lower the electronegativity of R, the slower the rearrangement.…”

Section: Imentioning

confidence: 89%

“…In this paper we report the cycloaddition reactions of SNS' with aryl nitriles and diphenylacetylene, (2,6,7). However, we were able to isolate small amounts of -CH,CNSNS.…”

Section: Introductionmentioning

confidence: 92%

See 1 more Smart Citation

Cycloaddition reactions of SNSAsF₆ with aryl nitriles and diphenylacetylene; the preparation and characterization of aryl 1,3,2,4- and 1,2,3,5-dithiadiazole radicals

Passmore¹,

Sun²,

Parsons³

1992

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The SNS+ cation (in SNSAsF6) underwent symmetry-allowed concerted cycloadditions with the aryl nitriles RCN (R = 2,5-Me2C6H3, Ph, p-O2NC6H4, and 3,5-(O2N)2C6H3) and diphenylacetylene. The cycloadducts [Formula: see text] (R = 2,5-Me2C6H3, Ph, p-O2NC6H4, and 3,5-(O2N)2C6H3) and Ph [Formula: see text] were characterized by elemental analyses and IR and NMR (1H, 13C, 14N) spectroscopies. The reduction of [Formula: see text] gave the corresponding 1,3,2,4-dithiadiazoles [Formula: see text], which in turn rearranged to the corresponding 1,2,3,5-dithiadiazoles [Formula: see text]. The rate of this rearrangement was correlated with the ionization potentials of the corresponding nitriles. The radicals [Formula: see text] (R = Ph, p-O2NC6H4) were isolated as pure compounds, and characterized by mass spectrometry, IR, FT-Raman, and ESR spectroscopies. The reduction of [Formula: see text] led to neutral radical [Formula: see text], which is stable in solution up to ca. 0.5 M, but decomposes at higher concentrations.

“…By means of some elegant ESR experiments they observed that the 1,3,2,4-dithiadiazolyl radical 24 could be photochemically converted to its more stable 1,2,3,5-isomer 25 (30). The reaction was shown to be second order in radical, and an orbital symmetry analysis of the proposed mechanism, which involved the centrosymmetric association and rearrangement of the resulting dimer (eq.…”

mentioning

confidence: 99%

1993 ALCAN Award Lecture Chemical binding within and between inorganic rings; the design and synthesis of molecular conductors

Oakley¹

1993

For a given number of skeletal atoms, the π-electron count of an unsaturated heterocycle can be modified by the incorporation of heteroatoms from different periodic groups. Sulfur and nitrogen are particularly effective in this regard, as their high electronegativity can stabilize electron-rich π-systems. A variety of aromatic, anti-aromatic, and radical systems can be prepared from admixtures of these elements. While the properties of these ring systems are interesting in their own right, the compounds are not without relevance in the design of new materials. The strong interannular interactions that are developed between these rings in the solid state makes them ideal candidates for the fabrication of molecular conductors. The origins and development of this area of research are the subjects of this presentation.