Increasing the electron donation in a dinucleating ligand family: molecular and electronic structures in a series of...

We have developed a family of dinucleating ligands with varying terminal donors to generate dinuclear peroxo and high-valent complexes and to correlate their stabilities and reactivities with their molecular and electronic structures as a function of the terminal donors. It appears that the electron-donating ability of the terminal donors is an important handle for controlling these stabilities and reactivities. Here, we present the synthesis of a new dinucleating ligand with potentially strong donating terminal imidazole donors. As Co^II ions are sensitive to variations in donor strength in terms of coordination number, magnetism, UV-Vis-NIR spectra, redox potentials, we probe the electron donation ability of this new ligand in Co^IICo^II complexes in comparison to the parent Co^IICo^II complexes with terminal pyridine donors and we synthesize the analogous Co^IICo^II complexes with terminal 6-methylpyridines and methoxy-substituted pyridines. The molecular structures show indeed strong variations in coordination numbers and bond lengths. These differences in the molecular structures are reflected in the magnetic properties and in the d-d transitions demonstrating that the molecular structures remain intact upon dissolution. The redox potentials are analyzed with respect to the electron donation ability and are the only handle to observe an effect of the methoxy-substituted pyridines. All data taken together show the following order of electron donating ability for the terminal donors: 6-methylpyridines ≪ pyridines < methoxy-substituted pyridines ≪ imidazoles.