Oligomeric Analogues of Polysulfur Nitride. 1. Reactions of Arylsulfenyl Chlorides with Bis(trimethylsilyl)sulfurdiimine

Reactions of [Me3SiNSNSiMe3] with [ArSC1] (Ar=4-MePh, 4-ClPh, 4-NO2Ph, 2-NO2Ph, 2,4-(NO2)2Ph) afforded 1-aryl-4-trimethylsilyl disulfur dinitrides [ArSNSNSiMe3] or 1,5-diaryl trisulfur dinitrides [ArSNSNSAr] with 1 or 2 equiv of [ArSCl], respectively. With 3 equiv of [ArSCl] (Ar=4-MePh, 4-ClPh) the novel compounds, 1,7-diaryl tetrasulfurtrinitrido chloride [ArSNSNSNSAr][Cl], were obtained. Mixed 1,5-diaryl trisulfur dinitrides were obtained from the reaction of [ArSNSNSiMe3] with [Ar1SCl] (Ar≠Ar1), whereas reactions of [ArSNSNSiMe3] (Ar=2-NO2Ph, 2,4-(NO2)2Ph) with [SCl2] resulted in the formation of 1,9-diaryl pentasulfur tetranitrides [ArSNSNSNSNSAr], The latter compounds have the longest chain of consecutive sulfur and nitrogen atoms reported for nonpolymeric molecules. The compounds were investigated with UV, IR, and 1H NMR spectroscopy. An increasing red shift was observed for the longest wavelength absorption in the UV-vis with increasing sulfur-nitrogen chain length, indicating extensive electron delocalization along the chain. © 1977, American Chemical Society. All rights reserved.