Dicobalt octacarbonyl in toluene solution can be quantitatively oxidized at room temperature with dibenzoyl peroxide to cobalt(II) benzoate and carbon monoxide. The rate of CO evolution is first order in dicobalt octacarbonyl, first order in dibenzoyl peroxide, and negative first order in CO. Similar behaviour leading to manganese(II) benzoate is observed with dimanganese decacarbonyl. Sixteen electron rather than seventeen electron intermediates are involved in these reactions. In contrast to the dinuclear carbonyls, Fe(CO)5 is oxidized by dibenzoyl peroxide in an autocatalytic reaction.
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Ungváry, F., Sisak, A. The oxidation of Co2(CO)8, Mn2(CO)10 and Fe(CO)5 by dibenzoyl peroxide. Kinetics and mechanism. Transition Met Chem 9, 265–267 (1984). https://doi.org/10.1007/BF00624470
- Physical Chemistry