Metal Induced Decarboxylation of Aliphatic Free Radicals. I. Kinetics of the Reactions of Copper(I) and Copper(II) Ions with the 2‐Methyl‐2‐Carboxylicacid‐Propyl Free Radical in Aqueous Solutions. A Pulse Radiolysis Study

CH 2 C(CH 3 ) 2 CO 2 H free radicals react with Cu 2+ aq to form Cu III ‐CH 2 C(CH 3 ) 2 CO 2 H 2+ aq , which probably is rapidly transformed into intermediate I. This intermediate decomposes into Cu + aq + CO 2 + CH 2 =C(CH 3 ) 2 . This is the first system in which a metal ion induced β‐carboxyl elimination reaction was observed. ·CH 2 C(CH 3 ) 2 CO 2 H free radicals react with Cu III ‐CH 2 C(CH 3 ) 2 CO 2 H 2+ aq to form Cu 2+ aq and a mixture of (‐CH 2 C(CH 3 ) 2 CO 2 H) 2 , (CH 3 ) 3 CCO 2 H, and HOCH 2 C(CH 3 ) 2 CO 2 H. CH 2 C(CH 3 ) 2 CO 2 H reacts with Cu + aq to form Cu II ‐CH 2 C(CH 3 ) 2 CO 2 H + aq . The latter intermediate decomposes both via homolysis and by a reaction with Cu 2+ aq to form 2Cu 2+ aq + (CH 3 ) 3 CCO 2 H. The spectra of the intermediates and the kinetics of reaction are reported.