Synthesis and ligand non-innocence of thiolate-ligated (N4S) iron(II) and nickel(II) bis(imino)pyridine complexes

The known iron(II) complex [FeII(LN3S)(OTf)] (1) was used as starting material to prepare the new biomimetic (N 4S(thiolate)) iron(II) complexes [FeII(LN 3S)(py)](OTf) (2) and [FeII(LN3S)(DMAP)](OTf) (3), where LN3S is a tetradentate bis(imino)pyridine (BIP) derivative with a covalently tethered phenylthiolate donor. These complexes were characterized by X-ray crystallography, ultraviolet-visible (UV-vis) spectroscopic analysis, 1H nuclear magnetic resonance (NMR), and Mössbauer spectroscopy, as well as electrochemistry. A nickel(II) analogue, [NiII(LN3S)](BF4) (5), was also synthesized and characterized by structural and spectroscopic methods. Cyclic voltammetric studies showed 1-3 and 5 undergo a single reduction process with E1/2 between -0.9 V to -1.2 V versus Fc+/Fc. Treatment of 3 with 0.5% Na/Hg amalgam gave the monoreduced complex [Fe(LN3S)(DMAP)] 0 (4), which was characterized by X-ray crystallography, UV-vis spectroscopic analysis, electron paramagnetic resonance (EPR) spectroscopy (g = [2.155, 2.057, 2.038]), and Mössbauer (δ = 0.33 mm s-1; ΔEQ = 2.04 mm s-1) spectroscopy. Computational methods (DFT) were employed to model complexes 3-5. The combined experimental and computational studies show that 1-3 are 5-coordinate, high-spin (S = 2) FeII complexes, whereas 4 is best described as a 5-coordinate, intermediate-spin (S = 1) FeII complex antiferromagnetically coupled to a ligand radical. This unique electronic configuration leads to an overall doublet spin (Stotal = 1/2) ground state. Complexes 2 and 3 are shown to react with O2 to give S-oxygenated products, as previously reported for 1. In contrast, the monoreduced 4 appears to react with O 2 to give a mixture of sulfur oxygenates and iron oxygenates. The nickel(II) complex 5 does not react with O2, and even when the monoreduced nickel complex is produced, it appears to undergo only outer-sphere oxidation with O2. © 2013 American Chemical Society.