The role of structural effects on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites. A time-resolved kinetic study.

A time-resolved kinetic study on the reactions of alkoxyl radicals with trialkyl and triaryl phosphites ((RO)(3)P: R = Me, Et, i-Pr, t-Bu; (ArO)(3)P: Ar = C(6)H(5), 2,4-(t-Bu)(2)C(6)H(3)) has been carried out. In the (RO)(3)P series, the alkoxyl radicals (cumyloxyl (CumO()) and benzyloxyl (BnO())) undergo addition to the phosphorus center with formation of intermediate tetraalkoxyphosphoranyl radicals (R'OP()(OR)(3): R = Me, Et, i-Pr, t-Bu; R' = Bn, Cum). The addition rate constants are influenced by steric effects, decreasing on going from R = Me to R = t-Bu and from BnO() to CumO(). Rate constants for beta-scission of the phosphoranyl radicals R'OP()(OR)(3) have also been determined, increasing, for a given alkyl group R, in the order R' = tert-butyl < R' = benzyl < R' = cumyl and, for a given R' group, on going from R = Me to R = i-Pr. This behavior has been explained in terms of the relative stability of the radicals formed after beta-scission, suggesting moreover that steric effects play in this case a minor role. CumO(*) reacts with triaryl phosphites (ArO)(3)P to give phenoxyl radicals, with rate constants that are influenced to a limited extent by substitution of the aromatic rings. The radical scavenging ability of these substrates is briefly discussed.