Structural, spectroscopic, and reactivity models for the manganese catalases.

Structural and functional models related to the nickel hydrogenases

Herein, we describe an uncommon example of a manganese-thiolate complex, which is capable of activating dioxygen and catalyzing its two-electron reduction to generate H2O2. The structurally characterized dimercapto-bridged Mn(II) dimer [Mn(II)2(LS)(LSH)]ClO4 (Mn(II)2SH) is formed by reaction of the LS ligand (2,2'-(2,2'-bipyridine-6,6'-diyl)bis(1,1-diphenylethanethiolate)) with Mn(II). The unusual presence of a pendant thiol group bound to one Mn(II) ion in Mn(II)2SH is evidenced both in the solid state and in solution. The Mn(II)2SH complex reacts with dioxygen in CH3CN, leading to the formation of a rare mono-μ-hydroxo dinuclear Mn(III) complex, [(Mn(III)2(LS)2(OH)]ClO4 (Mn(III)2OH), which has also been structurally characterized. When Mn(II)2SH reacts with O2 in the presence of a proton source, 2,6-lutidinium tetrafluoroborate (up to 50 equiv), the formation of a new Mn species is observed, assigned to a bis-μ-thiolato dinuclear Mn(III) complex with two terminal thiolate groups (Mn(III)2), with the concomitant production of H2O2 up to ∼40% vs Mn(II)2SH. The addition of a catalytic amount of Mn(II)2SH to an air-saturated solution of MenFc (n = 8 or 10) and 2,6-lutidinium tetrafluoroborate results in the quantitative and efficient oxidation of MenFc by O2 to afford the respective ferrocenium derivatives (MenFc(+), with n = 8 or 10). Hydrogen peroxide is mainly produced during the catalytic reduction of dioxygen with 80-84% selectivity, making the Mn(II)2SH complex a rare Mn-based active catalyst for two-electron O2 reduction.

Dioxygen Activation and Catalytic Reduction to Hydrogen Peroxide by a Thiolate-Bridged Dimanganese(II) Complex with a Pendant Thiol

Manganese(II) complexes with N,N′-bis(2-pyridylmethylene)-1,3-diaminopropan-2-ol (HL1) or N,N′-bis(2-pyridylmethylene)-1,3-propanediamine (L2), [Mn(HL1)(NO3)2] (1) and [Mn(HL1)(NCS)2] (2), [Mn(HL1)(phen)](ClO4)2 (3), [Mn2(L1)(CH3COO)(phen)2](ClO4)2 (4), [Mn(L2)(NO3)2] (5), [Mn(L2)(bpy)(CH3OH)](ClO4)2 (6), [Mn(L2)(NCS)2] (7), [Mn(L2)(phen)](ClO4)2 (8), have been synthesized and characterized by measurements of the infrared, electronic, and ESR spectra, and magnetic susceptibilities. The molecular structures of these complexes were determined by the single-crystal X-ray structure analysis. The complexes 1·C2H5OH and 5 have an eight-coordinated manganese atom with a square antiprism geometry. The complex 6 is seven-coordinated in a monocapped trigonal prism. The manganese atoms of 2, 7, and 8 are six-coordinated in a trigonal prism environment. The coordination environment of 3 is disordered between the seven- and six-coordinate geometries. The complex 4·H2O is a dinuclear molecule comprising two octahedral ...

Synthesis and Structural Characterization of Manganese(II) Complexes with N,N′-Bis(2-pyridylmethylene)-1,3-diaminopropan-2-ol or N,N′-Bis(2-pyridylmethylene)-1,3-propanediamine

Reactions of 3d-metal nitrates with N,N′-bis(2-pyridyl)urea (LH2): preparation, X-ray crystal structures and spectroscopic studies of the products trans-[M(II)(ONO2)2(LH2)2] (M=Mn, Fe, Co, Ni, Cu, Zn) and mer-[Co(III)(LH)2](NO3)·MeOH

Manganese(II) complexes with 2-[(2-aminoethyl)amino]ethanethiol (HLa), 2-[(3-aminopropyl)amino]ethanethiol (HLb), 2-[(2-pyridylmethyl)amino]ethanethiol (HLc), and 2-[[2-(2-pyridyl)ethyl]amino]ethanethiol (HLd)–[Mn(La)Cl]n (1), [Mn{Mn(Lb)2}2]Cl2·2CH3OH (2), [Mn(Lc)Cl]n (3), and [Mn(Ld)Cl(CH3OH)]n (4) have been synthesized and characterized by elemental analyses, infrared and electronic spectroscopies, and magnetic susceptibilities (80—300 K). The crystal structures of all these complexes were determined by the single-crystal X-ray diffraction method. Complexes 1 and 3 have a thiolate-bridged polymeric chain structure in which each manganese atom is five-coodinated in a trigonal bipyramid. Complex 2 is a thiolate-bridged trinuclear manganese(II) complex displaying a linear arrangement of the three manganese atoms with the two Mn–Mn interactions being equidistant [3.420(1) A]. Complex 4 is a thiolate-bridged polymeric infinite chain showing a distortion in the octahedral geometry around each manganese atom. ...

Syntheses and Characterization of Thiolate-Bridged Manganese(II) Complexes with NNS-Tridentate Thiolic Ligands

Thiolate-bridged complexes of iron(II) with 2-[(2-aminoethyl)amino]ethanethiol (HLa), 2-[(3-aminopropyl)amino]ethanethiol (HLb), and 2-[[2-(2-pyridyl)ethyl]amino]ethanethiol (HLc) — [Fe{Fe(La)2}2](ClO4)2·CH3OH (1), [Fe{Fe(Lb)2}2]Cl2·2CH3OH (2), and [Fe2(Lc)2(NO3)2] (3), respectively — have been synthesized and characterized by elemental analyses, and infrared and electronic spectroscopies as well as magnetic susceptibilities (80—300 K). The crystal structures of all of these complexes have been measured by single-crystal X-ray diffraction. Each of complexes 1 and 2 has a thiolate-bridged trinuclear iron(II) structure showing a linear arrangement of the three iron atoms with a geometry that may be described as Oh-Td-Oh. Complex 3 is a thiolate-bridged dinuclear iron(II) molecule, in which each iron atom is coordinated in a distorted octahedron. The electronic spectroscopic and magnetic properties are discussed in relation to the crystal structures.

Syntheses and Structural Characterization of Dinuclear and Trinuclear Iron(II) Complexes of Tridentate Thiolic Ligands with an NNS Donor Set.

Thiolate-bridged binuclear nickel(II) complexes with N,N-bis[2-(2-pyridyl)ethyl]-2-aminoethanethiol (HL), [Ni2(L)2](ClO4)2·1/2H2O and [Ni2(L)2](PF6)2, have been synthesized and characterized by elemental analyses, infrared and electronic spectra, and magnetic susceptibilities (80–300 K) The crystal structure of the perchlorate has been determined by the single-crystal X-ray diffraction method The [Ni2(L)2]2+ cation has a novel binuclear structure where one of the nickel ions is coordinated by a square-planar N2S2 donor set and the other has a distorted square-pyramidal configuration (N3S2 donor set) with the pendant pyridyl nitrogen at the apex From the above results, it was concluded that the present complexes are novel mixed-spin state containing a low-spin Ni(II) and a high-spin Ni(II) in the molecule

Thiolate-Bridged Binuclear Nickel(II) Complexes with a Mixed-Spin State.

A novel thiolate-bridged polynuclear manganese(II) complex with 2-[2-(2-pyridyl)ethylamino]ethanethiol

A mixed-valence tetranuclear vanadium(III, III, IV, IV) complex, [V2(VO)2(acac)4(CH3O)6] (Hacac = acetylacetone), has been isolated by a reaction of VO(acac)2 with 2-(3-aminopropylamino)ethanethiol in methanol-dichloromethane The complex has been characterized by X-ray structure analysis, XPS and electronic spectra, and magnetic susceptibilities (80–300 K)

A Tetranuclear Vanadium(III, III, IV, IV) Complex Formed by a Reaction of Bis(acetylacetonato)oxovanadium(IV) with a Thiolate Ligand

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