INTRAMOLECULAR REDOX CYCLIZATION UPON OXIDATION OF A SULFUR(II)-CONTAINING DIAZENE - X-RAY STRUCTURES OF PHS(O)NC(AR)NNC(AR)=NSO2PH (AR = 4-CH3C6H4) AND MESO2N(4-CH3C6H4)CN=NC(C6H4CH3-4)NSO2ME

The reaction of Z,E,Z-PhSN=C(Ar)N=NC(Ar)=NSPh (Ar = 4-CH3C6H4) (1a) wi th MCPB A results in ring closure via an intramolecular redox process to give the 1,2,3,5-thiatriazole PhS(O)NC(Ar)NNC(Ar)=NSO2Ph (4). An X- ray structural determination revealed that 4 contains a planar five-me mbered CNS(VI)NN ring with d(N-N) = 1.402(6) Angstrom. The reaction of ArCN2(SiMe3)(3) (Ar = 4-CH3C6H4) with one equivalent of MeSO2Cl, foll owed by two equivalents of PhSeCl, produces the sulfonyl-containing di azene MeSO2N=C(Ar)N=N(Ar)C=NSO2Me (11), which was shown by X-ray cryst allography to adopt a Z,E,Z geometry. By contrast, the reaction of ArC N2(SiM3)(3) with one equivalent of ArS(O)CI, followed by two equivalen ts of PhSeCl, yielded the sulfur(II)-containing diazene Z,E,Z-ArSN=C(A r)N=NC(Ar)=NSAr (Ar = 4-CH3C6H4) (1b).