Kinetics and mechanism of the outer-sphere oxidation of metal carbonyl anions with coordination complexes containing chloride

Article abstract of DOI:10.1021/om00038a013

Reactions of metal carbonyl anions, CpFe(CO)₂^-, Re(CO)₅^-, Mn(CO)₅^-, CpMo(CO)₃^-, CpCr(CO)₃^-, and Co(CO)₄^-, with CrCl₃·3S (S = THF, CH₃CN) and reactions of Mn(CO)₅^- and Re(CO)₅^- with [Co(o-phen)₂Cl₂]ClO₄ are reported. Net oxidation/reduction chemistry is observed with formation of metal carbonyl dimers and CrCl₂·4S or Co(o-phen)₂Cl₂. Metal carbonyl halides are also observed and shown to arise from a secondary reaction of the metal carbonyl dimer with the oxidant. The products and rates are most consistent with outer-sphere electron-transfer reactions. Reactions of CpFe(CO)₂^- with CpFe(CO)₂X (X = Cl, Br, I) are also reported. The rate dependence on X is very small and in the order expected for nucleophilic substitution.