Cobalt complexes, electron-transfer reactions carbonyl

The carbon dioxide anion radical was used for one-electron reductions of nitrobenzene diazonium cations, nitrobenzene itself, quinones, aliphatic nitro compounds, acetaldehyde, acetone and other carbonyl compounds, maleimide, riboflavin, and certain dyes (Morkovnik Okhlobystin 1979). This anion radical reduces organic complexes of Com and Rum into appropriate complexes of the metals in the valence 2 state (Morkovnik Okhlobystin 1979). In the case of the pentammino-p-nitrobenzoato-cobalt(III) complex, the electron-transfer reaction passes a stage of the formation of the Co(III) complex with the p-nitrophenyl anion radical fragment. This intermediate complex transforms into the final Co(II) complex with the p-nitrobenzoate ligand as a result of an intramolecular electron transfer. Scheme 1-89 illustrates this sequence of transformations ... 

Under a nitrogen atmosphere, cobalt carbonyl probably experiences disproportionation by base (Scheme 5) to give Co(CO)4. One of the disproportionation by-products is the Co(II) ion which gives a blue color in aqueous NaOH due to the presence of small amounts of the Co(OH)42-ion. The subsequent reaction of the cobalt tetracarbonyl anion with 14 is probably a displacement (path a), giving the cr-allyl complex 16. However, the possibility of an electron-transfer pathway (path b), either as an alternative to, or concurrent with, the displacement pathway cannot be dismissed at this time. 

His research interests include catalysis by cobalt, iron and manganese, complexes (biomimetic dioxygen activation, catalytic oxidation and carbonylation), as well as kinetics and mechanisms of inorganic reactions in solution (fast redox and electron transfer). 

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