Ligand replacement reactions of oxygen complexes of Cu+dipy2
By the stopped flow method it has been shown that acetate has no effect on the kinetics of the autoxidation of the dipyridyl complex of copper (I) (Cu+dipy2). Ethylenediaminetetraacetate effectively reacts with the oxygen adduct dipy2Cu+O2, malonic acid reacts with both the adduct and with the partial charge-transfer complex dipy2CuO2+.
The reaction of the dianion of malonic acid with the partial charge-transfer complex occurs by a mechanism of replacement of the coordinated 2,2′-dipyridyl and is accompanied by reduction of O2 to the Superoxide radical.
Reaction of polydentate ligands with the adduct also occurs by the mechanism of replacement of 2,2′-dipyridyl. When the adduct reacts with the monoanion of malonic acid, O2 is reduced to HO2. and when it reacts with the dianion O2 is reduced to O2.−.
The reaction rate constants for replacement of 2,2′-dipyridyl in the complexes dipy2Cu+O2 and dipy2CuO2+ have been determined, as well as the absolute values of the reaction rate constants of HO2 with Cu+dipy2 and Cu2+dipy2.
KeywordsOxygen Copper Acetate Superoxide Adduct
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