Synthesis, crystal structure and electrochemistry of cobalt(III) carboxamide complexes with amine and azide ancillary ligands

Six cobalt(III) complexes of the type [Co-III(Me(2)bpb)(amine)(N-3)] (Me(2)bpb(2-) = N,N'-(4,5-dimethyl-1,2-phenylene)dipicolinamide and amine = piperidine (pprdn) (I), pyrrolidine (prldn) (2), morpholine (mrpln) (3), pyridine (py) (4), 4-methylpyridine(4-Mepy) (5) and 4-acetylpyridine (4-Acpy) (6)) have been synthesized and characterized by elemental analyses, IR and UV-Vis spectroscopy. The structures of 1,3 and 4 have been determined by X-ray crystallography. Me(2)bpb(2-) is a dianionic tetradentate ligand, furnishing a N4 set, such that two N atoms of the two pyridine rings and two amido N atoms occupy four equatorial positions. The amine and azide ligands occupy the two axial positions, leading to a distorted octahedral geometry around the central cobalt ion. The electrochemical behavior of these complexes in DMF solution indicates that partial solvolysis of the complexes occurs and the axial amine ligand is replaced by DMF solvent in 1-6 leading to a [Co-III(Me(2)bpb)(DMF)(N-3)] species. The two additional redox processes observed in the cyclic voltammograms of these complexes originate from the oxidation of the 4,5-dimethylorthophenylene moiety of the Me(2)bpb(2-) ligand and a Co-III/II redox process in [Co-III(Me2- bpb)(DMF)(N-3)I. The Co-III/II redox potential of the [Co-III(Me(2)bpb)(amine)(N-3)] complexes is influenced by the nature of the axial amine ligand and varies from -0.53 for 4-Acpy to -0.79 V for pyrrolidine. (C) 2013 Elsevier Ltd. All rights reserved.