Structural and electron self-exchange rate variations in isomeric (hexaamine)cobalt(III/II) complexes

A novel method for the synthesis of a new macrocyclic hexaamine L6 and its hexadentate-coordinated CoIII complex was developed based on the reduction of the [CuL5]2+ complex. Analysis of the self-exchange electron transfer properties of the [CoL6]Cl2(ClO4) complex via X-ray crystallography indicated the presence of short Co-N bond lengths and a high-energy d-d electronic maxima. Furthermore, the CoIII/II self-exchange electron transfer rate constants of the complex exhibited marked variations in the disposition of its primary amino groups.