Reaction with transition metal ions

The thermodynamic functions (AH, AS, AG(298 K)) of hydrogen peroxide reactions with transition metal ions in aqueous solutions are presented in Table 10.1. We see that AG(298K) has negative values for reactions of hydroxyl radical generation with Cu1+, Cr2+, and Fe2+ ions and for reactions of hydroperoxyl radical generation with Ce4+, Co3+, and Mn3+. 

Rate Constants of Free Radical Reactions with Transition Metal Ions and Complexes... 

From the present point of view, the most important would be the further production of free radicals, most likely upon reaction with transition metal ions, for example... 

The 4,4 -bipyridine ligand has been utilized in the synthesis of linear coordination polymers as well as grids and networks through reaction with transition metal ions. These inorganic-organic polymers and frameworks are potential candidates for use in catalysis, molecular recognition, and nonlinear optics.257-262... 

Reactions of free radicals with molecules (or ions) can occur via an addition reaction, for instance the addition of a C-centered radical to oxygen (4.2), hydrogen atom abstraction (4.3), or electron transfer mechanism (e.g., oxidation of CO " by SO" ). Since the total number of electrons is odd, one of the products is a new radical (e.g., (4.2) and (4.3)), except for the reactions with transition metal ions, such as the oxidation of superoxide radicals by Fe3+ ions ... 

Some Properties of Dioxygen and its Reaction with Transition Metal Ions... 

Another possibility for the formation of free radical species from hypochlorite is through its reactions with transition metal ions. Thus, Guilmet and Meunier (1980) reported a manganese-promoted epoxidation of olefins such as styrene (Equation 5.13) and cyclohexene in a two-phase dichloromethane-water solvent mixture. The epoxide oxygen was derived from HOCl, not from air, but no mechanistic details were speculated upon. Further evidence needs to be obtained on the possibility of free-radical reactions in water and wastewater chlorination. 

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