Reactions of Thianthrene and 10-Phenylphenothiazine with the Lewis Acids─Titanium Tetrachloride, Titanium Tetrabromide, Tin(IV) Tetrachloride, or Antimony(V) Pentachloride: The Competition between Coordination and Oxidation.

The oxidation of thianthrene and 10-phenylphenothiazine into cation radicals has been examined using redox-active Lewis acids. The reaction of titanium(IV) tetrachloride with thianthrene in toluene produces a solution with an EPR spectrum indicative of oxidation of thianthrene to a cation radical, but the molecular compound (1) (μ-thianthrene)Ti2(μ-Cl2)Cl6 crystallized exclusively. Red crystalline (2) (μ-thianthrene)Ti2(μ-Br2)Br6 formed similarly from titanium(IV) tetrabromide. In contrast, the reaction of antimony(V) pentachloride with thianthrene in toluene yielded crystalline (3) (thianthrene·+)2(Sb2(μ-Cl)2Cl62-)·(SbCl3), while the same reaction in acetonitrile produced crystals of (4) (thianthrene·+)(SbCl6-). The two paramagnetic salts differ in that in (3), the folded (thianthrene·+) cation radicals self-associate, whereas in (4), the (thianthrene·+) cation radicals are isolated from one another and are planar. The reaction of 10-phenylphenothiazine with titanium(IV) tetrachloride in toluene solution resulted in the formation of crystalline paramagnetic (5) (10-phenylphenothiazine·+)(Ti(μ-Cl)3Cl6-) and the reaction of 10-phenylphenothiazine with tin(IV) tetrachloride produced paramagnetic (6) (10-phenylphenothiazine·+)(SnCl5-).