Radical formation during the reaction of bis(fluorosulfuryl)peroxide, S2O6F2, with tetrasulfur tetranitride, S4N4, and elemental sulfur, S8

The radical intermediates formed initially in the reaction of S2O6F2 with S4N4 and S8 have been studied by ESR spectroscopy at X-band level. The transient radical formed in the reaction between S2O6F2 and S4N4 has the spin Hamiltonian parameters gxx=2.0014, gyy=2.0054, gzz=2.0249, Axx=22.5 MHz, Ayy=4.5 MHz, Azz=2.0 MHz and Qzz=4 MHz as determined by simulation of ESR lineshapes obtained from polycrystalline samples. The spin Hamiltonian parameters are very similar to those previously reported for [S3N2]+·, and the spectra are interpreted as being most likely due to the [S3N2]+· radical. The reaction between S2O6F2 and S8 under similar conditions produces a radical that has a g-tensor of the form gxx=2.0026, gyy=2.0184, gzz=2.0258, as determined by simulation. The transient species generated is postulated to be a similar S5+· radical.