Electronically varied manganese tris-arylacetamide tripodal complexes

This report details the synthesis and characterization of six new Mn(II) complexes coordinated to systematically varied 2,2',2''-nitrilotris(N-arylacetamidate) ligands (LR; R = NO2, Cl, Br, H, Me, and OMe). The complexes are synthesized as the di-tetramethylammonium salts [Me4N]2[MnLR(OAc)]. The nitro variant MnNO2 afforded crystals suitable for X-ray diffraction and its molecular structure is reported. We previously reported the crystal structures of FeNO2 and ZnNO2 and additionally report herein the synthesis and characterization of CoNO2. Using these four molecules, we conduct a brief comparison of the bond metrics to demonstrate that the primary difference governing structural changes is likely due to ionic crystal radii changes rather than electronic properties. The electrochemical properties of the MnR complexes were additionally explored with cyclic voltammetry, which revealed that the series is modulated by the various electronic substituents on the aryl groups of the ligands. The electrochemical studies also revealed, consistent with our previous report, that the acetate ligand on the MnR complexes is labile. Finally, a Hammett plot was constructed using the potentials obtained from cyclic voltammetry, which is compared with a few other similar transition metal complexes.