Oxidation of the tetraarylpinacols (Ar(2)COH)(2), 1a-e, in which Ar = C(6)H(5) (1a), 4-ClC(6)H(4) (1b), 4-MeC(6)H(4) (1c), 4-MeOC(6)H(4) (1d) and 4-Me(2)NC(6)H(4) (1e), by thianthrene cation radical (Th(*+)) in CH(3)CN and in CH(2)Cl(2) led quantitatively to the corresponding diaryl ketones Ar(2)C=O (2a-e), provided a sufficient amount of base, 2,6-di-tert-butyl-4-methylpyridine (DTBMP), was present to prevent presumed acid-catalyzed rearrangement. In the case of 1e, continued oxidation of 2e was also observed. Oxidation of 1a by (4-BrC(6)H(4))(3)N(*+)SbCl(6)(-) and (4-BrC(6)H(4))(3)N(*+)SbF(6)(-) (Ar(3)N(*+)) occurred analogously. Evidence for the catalytic, cation-radical rearrangement of 1a by Ar(3)N(*+) (reported in earlier literature) and by Th(*+) could not be found. Quantitative oxidation of 1a to 2a and of 1d to 2d was obtained also with NOBF(4), again provided that sufficient DTBMP was present to prevent acid-catalyzed rearrangement. Catalytic, oxidative rearrangement of 1d at room temperature and (as reported in earlier literature) at -5 degrees C was not observed. Oxidation was also observed of 2,3-diphenyl-2,3-butanediol (3) to acetophenone (9) and of 1,1-dimethyl-2,2-diphenylethanediol (4) to 2a and acetone by Th(*+). Oxidation of 2,3-dimethyl-2,3-butanediol (5) by Th(*+) was not observed. Instead, even in the presence of DTBMP, pinacolone (10) and tetramethyloxirane (11) were formed, through, it is proposed, a mechanism involving complexation with Th(*+).