Experimental and Theoretical Investigations of the Formation of the Diazene PhSNC(H)NNC(H)NSPh from HCN2(SPh)3 by a Thiyl-Radical-Catalyzed Mechanism: Identification of the HC(NSPh)2 • Radical and X-ray Structures of HCN2(SPh)3 and PhSNC(H)NNC(H)NSPh

The reaction of HCN(2)(SiMe(3))(3) with benzenesulfenyl chloride in a 1:3 molar ratio produces HCN(2)(SPh)(3) (4) as thermally unstable, colorless crystals. The decomposition of (4) in toluene at 95 degrees C was monitored by UV-visible, (1)H NMR and ESR spectroscopy. The major final products of the decomposition were identified as PhSN=C(H)N=NC(H)=NSPh (5) and PhSSPh. The structures of 4 and 5 were determined by X-ray crystallography. The …