Stopped-flow kinetics studies reveal pH dependence of hydrogen peroxide oxidation in manganese carbonyls, suggesting new redox mechanisms for CO delivery.
Reported are stopped-flow kinetics studies of the hydrogen peroxide reaction with the water-soluble manganese(I) carbonyl complex. fac-[Mn(CO)3(Br)(bpCO2)]2- (I, bpCO22- = 2,2'-bipyridine-4,4'-dicarboxylate dianion) in alkaline solution. In an earlier study, the H2O2 oxidation of I was shown to be accompanied by the release of more than two equivalents of carbon monoxide. The stopped-flow studies here confirm the strongly pH dependence of the reaction rate, and a revised mechanism for this kinetics behavior is proposed. The larger interest in these systems derives from evaluating redox mechanisms for CO delivery from metal-based carbon monoxide releasing moieties (CORMs) under physiologically relevant conditions.
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Robison et al. (2025) studied this question.
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