Unstable intermediates. Part LXXIII. E.s.r. studies of peroxyl radicals formed from vanadium(V)

Abstract

A paramagnetic species formed by the interaction of peroxides with various vanadium compounds is thought to contain the unit V–OO, in which the unpaired electron is confined to the oxygen atoms. The principal values of the g-tensor are close to those for HO₂ and organic peroxyl radicals, and the ⁵¹V hyperfine tensor values show that the spin-density on vanadium is indirect, probably stemming from spin polarisation of the V–O σ-electrons. The results are compared with those for similar species derived from titanium and aluminium.