Octahedral Co(III) complexes of 2-(phenylimino)pyrrolyl ligands: Synthesis and structural characterisation

The reactions of CoCl₂ with three equivalents of 2-(phenylimino)pyrrolyl sodium salts, performed under a nitrogen atmosphere, lead to the formation of the Co(III) complexes Co(κ²N,N′-NC₄H₃C(H)N-C₆H₅)₃] (2a), Co(κ²N,N′-NC₄H₃C(CH₃)N-C₆H₅)₃] (2b) and Co(κ²N,N′-NC₁₆H₉C(H)N-C₆H₅)₃] (2c), accommodating three chelating iminopyrrolyl ligands. Complexes 2a-c were obtained in moderate yields, and their characterisation by ¹H, ¹³C NMR and X-ray diffraction show they are diamagnetic and have an octahedral geometry about the cobalt centre, respectively. Uncharacterised products were obtained in the same reaction involving ligand precursors such as 2-(2,6-dimethylphenylimino)pyrrolyl sodium salts, which is attributed to a greater steric hindrance in the coordination of three of these bulkier ligands. The redox behaviour of complexes 2a-c shows an irreversible reduction wave with a peak potential in the range −3.2 to −3.7 V. Upon reduction, the complexes decompose giving rise, in the case of 2a, to a redox pattern compatible with the formation of Co(κ²N,N′-NC₄H₃C(H)N-C₆H₅)₂].