Redox chemistry of cobalamin and its derivatives

• The first review focused solely on redox reactivity of cobalamins.
• Challenging activation of organocobalamins and cobalamin(II).
• Superior reactivity of cobalamin(II) toward free radicals.
• Super-nucleophilicity of cobalamin(I) and its high reducing properties.

A comprehensive review on redox reactions of Co(III), Co(II) and Co(I) forms of cobalamins (vitamin B12) and their derivatives (cobinamide, cobyrinates) is presented. An influence of coordination environment of cobalt ion on reactivity of corresponding species is discussed. Mechanisms of reduction of Co(III) and Co(II) species as well as oxidation of Co(II) and Co(I) complexes are given in terms of their in vivo and catalytic implications.

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