The cathodic reduction of nine ‘Costa-type’ organocobalt B12 model compounds, [RCo(III)L]C1O4 (where R = alkyl ligand; L = N2,N2′-propanediylbis- (2,3-butanedione 2-imine 3-oxime) and a neutral base), was studied in acetonitrile solvent, using cyclic voltammetry, controlled potential coulometry, and spectroelectrochemical techniques. The effect of the alkyl substituents, namely i-C3H7, neo-C5H11, i-C4H9, CH3CH2, C6H5CH2, CH3, HO(CH2)2, CH3- COOCH2 and CF3CH2, on the relevant cobalt reduction mechanisms and potentials was investigated. A marked infiuence of axial group bulk on the reactivity of the low oxidation state cobalt derivatives formed in the reduction process has been evidentiated. The reactivity of these electrogenerated compounds is conditioned for the most part by their ability to form stable bisalkyl complexes.
Electrochemical behavior of ‘costa-type’ organocobalt coenzyme B12 models / Seeber, Renato; Roberto, Marassi; Wallace O., Parker; G., Kelly. - In: INORGANICA CHIMICA ACTA. - ISSN 0020-1693. - STAMPA. - 168:(1990), pp. 127-138. [10.1016/S0020-1693(00)88027-5]
Electrochemical behavior of ‘costa-type’ organocobalt coenzyme B12 models
SEEBER, Renato;
1990
Abstract
The cathodic reduction of nine ‘Costa-type’ organocobalt B12 model compounds, [RCo(III)L]C1O4 (where R = alkyl ligand; L = N2,N2′-propanediylbis- (2,3-butanedione 2-imine 3-oxime) and a neutral base), was studied in acetonitrile solvent, using cyclic voltammetry, controlled potential coulometry, and spectroelectrochemical techniques. The effect of the alkyl substituents, namely i-C3H7, neo-C5H11, i-C4H9, CH3CH2, C6H5CH2, CH3, HO(CH2)2, CH3- COOCH2 and CF3CH2, on the relevant cobalt reduction mechanisms and potentials was investigated. A marked infiuence of axial group bulk on the reactivity of the low oxidation state cobalt derivatives formed in the reduction process has been evidentiated. The reactivity of these electrogenerated compounds is conditioned for the most part by their ability to form stable bisalkyl complexes.
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