Reactions of Low-Valent Transition-Metal Complexes with Hydrogen Peroxide. Are They “Fenton-like” or Not? 1. The Case of Cu+aq and Cr2+aq

Mohamed Masarwa, Haim Cohen, Dan Meyerstein, David L. Hickman, Andreja Bakac, James H. Espenson

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Abstract

A thermodynamic analysis of the Fenton reaction and the “Fenton-like” reactions points out that their detailed mechanisms involve the formation of a transient complex between the low-valent cation MLmn and hydrogen peroxide of the type MLm-1n·O2H-. This complex might decompose into MLmn+1 + ·OH or MLmn+2 + H2O or react directly with a substrate. Experimental data from studies in acidified solutions indicate that (H2O)5Cr2+·O2H- decomposes into Cr(H2O)63++ ·OH in the presence of ≥0.1 M ethanol, 2-propanol, and 2-butanol, whereas (H2O)mCu+·O2H- reacts with the alcohols directly. However, in the absence of an organic substrate, the latter complex in acidic solution decomposes into Cu(H2O)n2+ + ·OH. The specific overall reaction rates of Cu+aq with H2O2, (CH3)3COOH, and S2O82- are 4.1 × 103, ~4 × 103, and ≥1 × 107M-1s-1, respectively.

Original languageEnglish
Pages (from-to)4293-4297
Number of pages5
JournalJournal of the American Chemical Society
Volume110
Issue number13
DOIs
StatePublished - Jun 1988
Externally publishedYes

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