Two-step binding of O2 to a vanadium(III) trisanilide complex to form a non-vanadyl vanadium(V) peroxo complex

Treatment of V(N[(t)Bu]Ar)(3) (1) (Ar = 3,5-Me(2)C(6)H(3)) with O(2) was shown by stopped-flow kinetic studies to result in the rapid formation of (η(1)-O(2))V(N[(t)Bu]Ar)(3) (2) (ΔH(‡) = 3.3 ± 0.2 kcal/mol and ΔS(‡) = -22 ± 1 cal mol(-1) K(-1)), which subsequently isomerizes to (η(2)-O(2))V(N[(t)Bu]Ar)(3) (3) (ΔH(‡) = 10.3 ± 0.9 kcal/mol and ΔS(‡) = -6 ± 4 cal mol(-1) K(-1)). The enthalpy of binding of O(2) to form 3 is -75.0 ± 2.0 kcal/mol, as measured by solution calorimetry. The reaction of 3 and 1 to form 2 equiv of O≡V(N[(t)Bu]Ar)(3) (4) occurs by initial isomerization of 3 to 2. The results of computational studies of this rearrangement (ΔH = 4.2 kcal/mol; ΔH(‡) = 16 kcal/mol) are in accord with experimental data (ΔH = 4 ± 3 kcal/mol; ΔH(‡) = 14 ± 3 kcal/mol). With the aim of suppressing the formation of 4, the reaction of O(2) with 1 in the presence of (t)BuCN was studied. At -45 °C, the principal products of this reaction are 3 and (t)BuC(═O)N≡V(N[(t)Bu]Ar)(3) (5), in which the bound nitrile has been oxidized. Crystal structures of 3 and 5 are reported.