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Issue 4, 2011
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A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical

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Abstract

Reaction of 1,4-naphthoquinone and SNSMF6 (M = As, Sb) in SO2 solution in a 1 : 2 molar ratio led to the naphthoquinone fused 1,3,2-dithiazolylium salts, 3MF6 quantitatively by multinuclear NMR (87% isolated yield of 3SbF6) via the cycloaddition and oxidative dehydrogenation chemistry of SNS+ with formation of NH4SbF6 and S8. The product 3SbF6 was fully characterized by IR, Raman, multinuclear {1H, 13C, 14N} NMR, elemental analysis, cyclic voltammetry and single crystal X-ray crystallography. The reduction of 3SbF6 with ferrocene (Cp2Fe) in refluxing acetonitrile (CH3CN) led to the first isolation of a fused quinone-thiazyl radical, 3˙ in 73% yield. The prototype hybrid quinone-thiazyl radical 3˙ was fully characterized by IR, Raman microscopy, EI-MS, elemental analysis, solution and solid state EPR, magnetic susceptibility (2–370 K) and was found to form π*–π* dimers in the solid state as determined by single crystal X-ray crystallography. Furthermore, the thermal decomposition of 3˙ led to a novel quinone-fused 1,2,3,4-tetrathiine, 10 (x = 2) and the known 1,2,5-thiadiazole, 11. The energetics of the cycloadditon and oxidative dehydrogenation chemistry of SNS+ and 1,4-naphthoquinone leading to 3SbF6 were estimated in the gas phase and SO2 solution by DFT calculations (PBE0/6-311G(d)) and lattice enthalpies obtained by the volume based thermodynamic (VBT) approach in the solid state. The gas phase ion energetics (ionization potential (IP) and electron affinity (EA)) of 3˙ are compared to related 1,3,2- and 1,2,3-dithiazolyl radicals.

Graphical abstract: A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical

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Publication details

The article was received on 05 Aug 2010, accepted on 01 Nov 2010 and first published on 09 Dec 2010


Article type: Paper
DOI: 10.1039/C0DT00967A
Citation: Dalton Trans., 2011,40, 868-879
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    A prototype hybrid 7π quinone-fused 1,3,2-dithiazolyl radical

    A. Decken, A. Mailman, J. Passmore, J. M. Rautiainen, W. Scherer and E.-W. Scheidt, Dalton Trans., 2011, 40, 868
    DOI: 10.1039/C0DT00967A

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