Electrochemical properties of [FeIII(L)2Cl2][PF6] and [Fe2III,IIIO(L)4Cl2][PF6]2 [L=2,2′-bipyridine (bpy) and 4,4′-dimethyl-2,2′-bipyridine (dmbpy)]. Crystal structures of the dmbpy derivatives

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Abstract
The electrochemical behaviour of the iron(III) complexes [Fe(L)2Cl2]+ and [Fe2O(L)4Cl2]2+ [L=2,2′-bipyridine (bpy) and 4,4′-dimethyl-2,2′-bipyridine (dmbpy)] has been investigated in acetonitrile. Their reduction leads to the iron(II) complex ion [Fe(L)3]2+, accompanied by the release of Cl- ions and the formation of [FeCl4]- ions or by the formation of an unidentified Fe(III) chloro oxide, depending on the starting complex. These two new chloro complexes can be further reduced into Fe(II) species at a more negative potential. In addition, it has been shown that [Fe(L)2Cl2]+ can be obtained in good yield via the electrochemical oxidation of [Fe(L)3]2+ in the presence of free Cl- anions, at least for L=dmbpy. The crystal structure of the new mono- and binuclear dmbpy complexes has been determined by X-ray diffraction.

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