Low-spin [MII(L)2] and [MIII(L)2]+ (M = Fe and Co) complexes of tridentate azo-containing pyridine/pyrazine amide ligands: structures, properties and redox potential correlations

Abstract

Using deprotonated forms of tridentate azo-containing pyridine-2-/pyrazine-2-carboxamide 2-[N-(2-phenylazo)carbamoyl]-pyridine/pyrazine, seven bis-ligand complexes of Fe^II/Co^II and Fe^III/Co^III have been synthesized. Molecular structures of six of them reveal that these six-coordinate complexes utilize all available donor sites of the ligands and assume M^II/IIIN₂(pyridine/pyrazine)N′₂(amide)N′′₂(azo) coordination. Complexes of Fe^II and Co^III are diamagnetic and those of Fe^III and Co^II are paramagnetic (S = 1/2; room-temperature magnetic data and EPR spectra). Cyclic voltammetry experiments in CH₂Cl₂ reveal facile metal-centred Fe^III/Fe^II and Co^III/Co^II redox responses, and all complexes display quasireversible-to-irreversible ligand(azo)-centred redox processes. The E_1/2 values of M^III/M^II redox processes for Fe, Co and Ni (reported earlier) complexes of the pyridine amide ligand linearly correlate with those for six-coordinate [M^III(bpy)₃]³⁺/[M^II(bpy)₃]²⁺, [M^III(terpy)₂]³⁺/[M^II(terpy)₂]²⁺, [M^III(L)]⁺/[M^II(L)]⁰ or [M^III(L′)₂]⁺/[M^II(L′)₂]⁰ (bpy = 2,2′-bipyridine, terpy = 2,2′:6′,2′′-terpyridine, hexadentate L(2−) = 1,4-bis[o-(pyridine-2-carboxamidophenyl)]-1,4-dithiobutane and tridentate L′(−) = {2-[2-(arylimino)phenylazo]-pyridine}) couples. Density functional theory (DFT) at the B3LYP level and time-dependent (TD)-DFT calculations rationalize the electronic structure of the present complexes and throw light on the origin of observed electronic transitions.