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

Abstract The radical intermediates formed initially in the reaction of S 2 O 6 F 2 with S 4 N 4 and S 8 have been studied by ESR spectroscopy at X-band level. The transient radical formed in the reaction between S 2 O 6 F 2 and S 4 N 4 has the spin Hamiltonian parameters g xx =2.0014, g yy =2.0054, g zz =2.0249, A xx =22.5 MHz, A yy =4.5 MHz, A zz =2.0 MHz and Q zz =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 [S 3 N 2 ] +· , and the spectra are interpreted as being most likely due to the [S 3 N 2 ] +· radical. The reaction between S 2 O 6 F 2 and S 8 under similar conditions produces a radical that has a g -tensor of the form g xx =2.0026, g yy =2.0184, g zz =2.0258, as determined by simulation. The transient species generated is postulated to be a similar S 5 +· radical.