RADICAL FORMATION DURING THE REACTION OF BIS(FLUOROSULFURYL)PEROXIDE, S2O6F2, WITH TETRASULFUR TETRANITRIDE, S4N4, AND ELEMENTAL SULFUR, S-8

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 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 [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 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 S5+. radical.