Benzo-Bridged Bis(1,2,3-dithiazoles) and Their Selenium Analogues. Preparation, Molecular and Electronic Structures, and Redox Chemistry

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Abstract

The condensation of diaminobenzenedithiol with sulfur monochloride leads to the chloride salt of the radical cation of 3,6-dichlorobenzo[1,2-d:4,5-d‘]bis(1,2,3-dithiazole), dichloro-[BB-123-DTA][Cl], which can be reduced to neutral dichloro-[BB-123-DTA] with triphenylantimony. A similar condensation with selenium tetrachloride leads, upon reduction, to the corresponding bis(1,2,3-thiaselenazole) dichloro-[BB-123-TSA]. The crystal and molecular structures of both compounds have been determined by X-ray diffraction. Both compounds, which are formally antiaromatic 16π-systems, exhibit internal bond lengths consistent with a quinoid formulation. The radical cations of both rings have been characterized by ESR spectroscopy; for dichloro-[BB-123-DTA]+ g = 2.0114 and aN = 0.201 mT, while for dichloro-[BB-123-TSA]+ g = 2.021 and aN = 0.44 mT. Further oxidation of both rings affords the corresponding dications, both of which have been characterized crystallographically as their AlCl4- salts. The structural features of these compounds are consistent with those expected for dithiazolylium (or thiaselenazolylium) derivatives. The structure and redox chemistry of the benzo[1,2-d:4,5-d‘]bis(1,2,3-dithiazole) framework is discussed in the light of the results of ab initio calculations.

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