The reaction of HCN2(SiMe(3))(3) with benzenesulfenyl chloride in a 1:3 molar ratio produces HCN2(SPh)(3) (4) as thermally unstable, colorless crystals. The decomposition of (4) in toluene at 95 degrees C was monitored by UV-visible, H-1 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 crystals of 4 are monoclinic, space group P2(1)/a, with a = 9.874(2) Angstrom, b = 19.133(2) degrees, c = 10.280(2) Angstrom, beta = 113.37(1)degrees, V = 1782.8(5) Angstrom(3), and Z = 4. The final R and R(w) values were 0.042 and 0.049, respectively.