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The reactions of thianthrene (TA) and selenanthrene (SeA) with AlCl3 were studied in the melt phase and with liquid SO2 as solvent. From neat AlCl3 and TA, the colorless complex [AlCl3(TA)] was isolated as the main product and the dark red salt (TA)3[Al2Cl7]2 as the byproduct. The analogous solvent‐free reaction of selenanthrene and AlCl3 takes a different course as colorless [Al(SeA)3][Al2Cl7]3 is...
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