Influence of the second coordination sphere on O activation by a nonheme iron(II) thiolate complex.

The synthesis and characterization of a new ligand, 1-(bis(pyridin-2-ylmethyl) amino)-2-methylpropane-2-thiolate (BPAS) and its nonheme iron complex, Fe(BPAS)Br (1), is reported. Reaction of 1 with O at -20 °C generates a high-spin iron(III)-hydroxide complex, [Fe(OH)(BPAS)(Br)] (2), that was characterized by UV-vis, Fe Mössbauer, and electron paramagnetic resonance (EPR) spectroscopies, and electrospray ionization mass spectrometry (ESI-MS). Density functional theory (DFT) calculations were employed to support the spectroscopic assignments.