title: Mononuclear, Dinuclear, and Trinuclear Iron Complexes Featuring a New Monoanionic SNS Thiolate Ligand.
abstract: The new tridentate ligand, S(Me)N(H)S = 2-(2-methylthiophenyl)benzothiazolidine, prepared in a single step from commercial precursors in excellent yield, undergoes ring-opening on treatment with Fe(OTf)2 in the presence of base affording a trinuclear iron complex, [Fe3(μ2-S(Me)NS(-))4](OTf)2 (1) which is fully characterized by structural and spectroscopic methods. X-ray structural data reveal that 1 contains four S(Me)NS(-) ligands meridionally bound to two pseudooctahedral iron centers each bridged by two thiolates to a distorted tetrahedral central iron. The combined spectroscopic (UV-vis, Mössbauer, NMR), magnetic (solution and solid state), and computational (DFT) studies indicate that 1 includes a central, high-spin Fe(II) (S = 2) with two low-spin (S = 0) peripheral Fe(II) centers. Complex 1 reacts with excess PMePh2, CNxylyl (2,6-dimethylphenyl isocyanide), and P(OMe)3 in CH3CN to form diamagnetic, thiolate-bridged, dinuclear Fe(II) complexes {[Fe(μ-S(Me)NS(-))L2]2}(OTf)2 (2-4). These complexes are characterized by elemental analysis; (1)H NMR, IR, UV-vis, and Mössbauer spectroscopy; and single crystal X-ray diffraction. Interestingly, addition of excess P(OMe)3 to complex 1 in CH2Cl2 produces primarily the diamagnetic, mononuclear Fe(II) complex, {Fe(S(Me)NS(-))[P(OMe)3]3}(OTf) (5).
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Uttam K
authors.initials: UK
authors.lastname: Das
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Stephanie L
authors.initials: SL
authors.lastname: Daifuku
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Serge I
authors.initials: SI
authors.lastname: Gorelsky
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Ilia
authors.initials: I
authors.lastname: Korobkov
authors.affiliation: Department of Chemistry, University of Rochester , Rochester, New York 14627, United States.
authors.forename: Michael L
authors.initials: ML
authors.lastname: Neidig
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Jennifer J
authors.initials: JJ
authors.lastname: Le Roy
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , Ottawa, Ontario K1N 6N5, Canada.
authors.forename: Muralee
authors.initials: M
authors.lastname: Murugesu
authors.affiliation: Department of Chemistry and Biomolecular Sciences and Centre for Catalysis Research and Innovation, University of Ottawa , Ottawa, Ontario K1N 6N5, Canada.
authors.forename: R Tom
authors.initials: RT
authors.lastname: Baker