CH2C(CH3)2CO2H free radicals react with Cu2+aq to form CuIII‐CH2C(CH3)2CO2H2+aq, which probably is rapidly transformed into intermediate I. This intermediate decomposes into Cu+aq + CO2 + CH2=C(CH3)2. This is the first system in which a metal ion induced β‐carboxyl elimination reaction was observed. ·CH2C(CH3)2CO2H free radicals react with CuIII‐CH2C(CH3)2CO2H2+aq to form Cu2+aq and a mixture of (‐CH2C(CH3)2CO2H)2, (CH3)3CCO2H, and HOCH2C(CH3)2CO2H. CH2C(CH3)2CO2H reacts with Cu+aq to form CuII‐CH2C(CH3)2CO2H+aq. The latter intermediate decomposes both via homolysis and by a reaction with Cu2+aq to form 2Cu2+aq + (CH3)3CCO2H. The spectra of the intermediates and the kinetics of reaction are reported.
ChemInform Abstract A thermodynamic analysis of the Fenton and "Fenton-like" reactions reveals that the detailed mechanism involve the formation of a transient complex between the low-valent MLn+ m cation and H2O2 of type MLn+ m-1•O2H-. This complex might decompose into ML(n+1)+ m and .OH radical, or into ML(n+2)+ m and H2O, or react directly with a substrate. For acidified solutions of (H2O)5Cr2+•O2H-, the first decomposition scheme is observed in the presence of ≥ 0.1 M ethanol, 2-propanol, and 2-butanol, whereas the corresponding Cu+ complex reacts directly with the alcohols. However, in the absence of an organic substrate, the Cu(I) complex also decomposes into Cu(aq)2+ and .OH radical in acidic solution. Specific overall reaction rates of the reactions of Cu(aq)+ with H2O2, Me3C-O-OH, and S2O82-are reported.
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