title: Sulfide Oxidation by O2: Synthesis, Structure and Reactivity of Novel Sulfide-Incorporated Fe(II) Bis(imino)pyridine Complexes.
abstract: The unsymmetrical iron(II) bis(imino)pyridine complexes [FeII(LN3SMe)(H2O)3](OTf)2(1), and [FeII(LN3SMe)Cl2] (2) were synthesized and their reactivity with O2 was examined. Complexes1and2were characterized by single crystal X-ray crystallography, LDI-MS,1H-NMR and elemental analysis. The LN3SMe ligand was designed to incorporate a single sulfide donor and relies on the bis(imino)pyridine scaffold. This scaffold was selected for its ease of synthesis and its well-precedented ability to stabilize Fe(II) ions. Complexes1and2ware prepared via a metal-assisted template reaction from the unsymmetrical pyridyl ketone precursor 2-(O=CMe)-6-(2,6-(iPr2-C6H3N=CMe)-C5H3N. Reaction of1with O2was shown to afford the S-oxygenated sulfoxide complex [Fe(LN3S(O)Me)(OTf)]2+(3), whereas compound2, under the same reaction conditions, afforded the corresponding sulfone complex [Fe(LN3S(O2)Me)Cl]2+(4).
authors.affiliation: Department of Chemistry, The Johns Hopkins University, 3400 N. Charles Street, Baltimore, MD 21218.
authors.forename: Leland R
authors.initials: LR
authors.lastname: Widger
authors.forename: Maxime A
authors.initials: MA
authors.lastname: Siegler
authors.forename: David P
authors.initials: DP
authors.lastname: Goldberg
keywords: bis(imino)pyridine; dioxygen; iron(II); sulfide; sulfone; sulfoxide