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 approximate density functional theory is used in conjunction with spectroscopic and x-ray crystallography measurements to study the thermodynamics associated with the decomposition of HCN2(SPh)3 by free radicals. Results show that the major products of the decomposition process are diazene and PhSSPh. The data also suggest that diazene is formed by a mechanism in which the RS radical acts as the catalyst.