Effect of Nitrilotriacetate on the Mechanism of Reduction of Copper(II) Ions by a-Hydroxyalkyl Free Radicals via Complexes with Copper-Carbon Bonds as Intermediates. A Pulse-Radiolytic Study

a-Hydroxyalkyl free radicals, ·CR₁R2OH, react with copper(II) nitrilotriacetate, Cu(nta)^-(aq), in aqueous solutions to form the unstable intermediates (nta)Cu^III-CR₁R₂OH-(aq), or (nta)Cu^III-CH_2O^2-(aq). These intermediates decompose by reducing a second Cu^II(nta)^-(aq) complex, i.e. via the reaction (nta)Cu^III-CR₁R₂OH-(aq) + Cu^II(nta)^-(aq) Cu^I(nta)^2-(aq) + Cu^II(nta)-(aq) + CR₁R₂O + H₃0⁺. Unexpectedly, the intermediates do not decompose via first-order processes as expected. The spectrum of (nta)Cu^III-CH₂OH-(aq) is reported. The kinetics of reduction of Co(NH₃)₆³⁺, Ru(NH₃)₆³⁺, and Fe(CN)₆^3-by the latter intermediate are reported.