Syntheses and properties of dinuclear group 6 metal complexes with the zwitterionic sulfur donor ligand bis(N, N -diethylamino) carbeniumdithiocarboxylate

Tomoaki Sugaya, Takeshi Ohba, Fumiya Sai, Shigeru Mashima, Takashi Fujihara, Kei Unoura, Akira Nagasawa

    Research output: Contribution to journalArticle

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    Abstract

    A class of dinuclear group 6 metal complexes [{M0(CO) 5}2(μ-S,S′-EtL)] (M = Cr, Mo, W) with the asymmetrically bridged zwitterionic sulfur donor bis(N,N-diethylamino) carbeniumdithiocarboxylate (EtL) was prepared by photoreaction of [M 0(CO)6] with EtL in hexane-CH2Cl2 for Cr and Mo or THF for W. The same structure in a syn-anti coordination mode was revealed by X-ray analyses for chromium(0) and tungsten(0) complexes, 1 and 3, respectively, and speculated from various analytical data for the molybdenum(0) complex 2. The pertinent criteria for the coordination mode are found to be the wavenumber of the asymmetric stretching vibration of the -CS2 moiety in the solid state and the ligand-based reduction potential in solution. Complexes 1 and 3 showed quasi-reversible reduction waves, which are assigned to a two-step, one-electron reduction process derived from the bridging EtL. In a series of [Cr(CO)5L] complexes (L = monodentate ligand), the 13C NMR chemical shifts of the trans-to-L carbonyl group showed the order of increasing σ-donor/π-acceptor ratio of the ligands. The sulfur donor ligands, including EtL and thione, are positioned in the middle of this range. All complexes exhibited negative solvatochromism: the wavelength of the absorption maximum shifted to the blue side in the range 500-600 nm with an increase in the Reichardt solvent polarity parameters ET(30), except for protic solvents. Quantum chemical calculations by time-dependent density functional theory-polarized continuum model were employed for understanding the excited states and solvatochromic properties of complex 3. The calculated vertical excitation energies in solution are consistent with the experimental data, suggesting that the transition is a metal-to-ligand charge-transfer transition. In addition, UV-vis, NMR, and cyclic voltammetry data showed that complex 3 dissociates into two mononuclear species in polar solvents: [W(CO)5(EtL)] and [W(CO)5(solvent)].

    Original languageEnglish
    Pages (from-to)3441-3450
    Number of pages10
    JournalOrganometallics
    Volume32
    Issue number12
    DOIs
    Publication statusPublished - 2013 Jun 24

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    Coordination Complexes
    Carbon Monoxide
    Sulfur
    sulfur
    Ligands
    ligands
    synthesis
    metals
    Nuclear magnetic resonance
    Thiones
    nuclear magnetic resonance
    Tungsten
    Molybdenum
    Excitation energy
    Chemical shift
    Hexanes
    Chromium
    Excited states
    Cyclic voltammetry
    Stretching

    ASJC Scopus subject areas

    • Organic Chemistry
    • Physical and Theoretical Chemistry
    • Inorganic Chemistry

    Cite this

    Syntheses and properties of dinuclear group 6 metal complexes with the zwitterionic sulfur donor ligand bis(N, N -diethylamino) carbeniumdithiocarboxylate. / Sugaya, Tomoaki; Ohba, Takeshi; Sai, Fumiya; Mashima, Shigeru; Fujihara, Takashi; Unoura, Kei; Nagasawa, Akira.

    In: Organometallics, Vol. 32, No. 12, 24.06.2013, p. 3441-3450.

    Research output: Contribution to journalArticle

    Sugaya, Tomoaki ; Ohba, Takeshi ; Sai, Fumiya ; Mashima, Shigeru ; Fujihara, Takashi ; Unoura, Kei ; Nagasawa, Akira. / Syntheses and properties of dinuclear group 6 metal complexes with the zwitterionic sulfur donor ligand bis(N, N -diethylamino) carbeniumdithiocarboxylate. In: Organometallics. 2013 ; Vol. 32, No. 12. pp. 3441-3450.
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    title = "Syntheses and properties of dinuclear group 6 metal complexes with the zwitterionic sulfur donor ligand bis(N, N -diethylamino) carbeniumdithiocarboxylate",
    abstract = "A class of dinuclear group 6 metal complexes [{M0(CO) 5}2(μ-S,S′-EtL)] (M = Cr, Mo, W) with the asymmetrically bridged zwitterionic sulfur donor bis(N,N-diethylamino) carbeniumdithiocarboxylate (EtL) was prepared by photoreaction of [M 0(CO)6] with EtL in hexane-CH2Cl2 for Cr and Mo or THF for W. The same structure in a syn-anti coordination mode was revealed by X-ray analyses for chromium(0) and tungsten(0) complexes, 1 and 3, respectively, and speculated from various analytical data for the molybdenum(0) complex 2. The pertinent criteria for the coordination mode are found to be the wavenumber of the asymmetric stretching vibration of the -CS2 moiety in the solid state and the ligand-based reduction potential in solution. Complexes 1 and 3 showed quasi-reversible reduction waves, which are assigned to a two-step, one-electron reduction process derived from the bridging EtL. In a series of [Cr(CO)5L] complexes (L = monodentate ligand), the 13C NMR chemical shifts of the trans-to-L carbonyl group showed the order of increasing σ-donor/π-acceptor ratio of the ligands. The sulfur donor ligands, including EtL and thione, are positioned in the middle of this range. All complexes exhibited negative solvatochromism: the wavelength of the absorption maximum shifted to the blue side in the range 500-600 nm with an increase in the Reichardt solvent polarity parameters ET(30), except for protic solvents. Quantum chemical calculations by time-dependent density functional theory-polarized continuum model were employed for understanding the excited states and solvatochromic properties of complex 3. The calculated vertical excitation energies in solution are consistent with the experimental data, suggesting that the transition is a metal-to-ligand charge-transfer transition. In addition, UV-vis, NMR, and cyclic voltammetry data showed that complex 3 dissociates into two mononuclear species in polar solvents: [W(CO)5(EtL)] and [W(CO)5(solvent)].",
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    AU - Sugaya, Tomoaki

    AU - Ohba, Takeshi

    AU - Sai, Fumiya

    AU - Mashima, Shigeru

    AU - Fujihara, Takashi

    AU - Unoura, Kei

    AU - Nagasawa, Akira

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    N2 - A class of dinuclear group 6 metal complexes [{M0(CO) 5}2(μ-S,S′-EtL)] (M = Cr, Mo, W) with the asymmetrically bridged zwitterionic sulfur donor bis(N,N-diethylamino) carbeniumdithiocarboxylate (EtL) was prepared by photoreaction of [M 0(CO)6] with EtL in hexane-CH2Cl2 for Cr and Mo or THF for W. The same structure in a syn-anti coordination mode was revealed by X-ray analyses for chromium(0) and tungsten(0) complexes, 1 and 3, respectively, and speculated from various analytical data for the molybdenum(0) complex 2. The pertinent criteria for the coordination mode are found to be the wavenumber of the asymmetric stretching vibration of the -CS2 moiety in the solid state and the ligand-based reduction potential in solution. Complexes 1 and 3 showed quasi-reversible reduction waves, which are assigned to a two-step, one-electron reduction process derived from the bridging EtL. In a series of [Cr(CO)5L] complexes (L = monodentate ligand), the 13C NMR chemical shifts of the trans-to-L carbonyl group showed the order of increasing σ-donor/π-acceptor ratio of the ligands. The sulfur donor ligands, including EtL and thione, are positioned in the middle of this range. All complexes exhibited negative solvatochromism: the wavelength of the absorption maximum shifted to the blue side in the range 500-600 nm with an increase in the Reichardt solvent polarity parameters ET(30), except for protic solvents. Quantum chemical calculations by time-dependent density functional theory-polarized continuum model were employed for understanding the excited states and solvatochromic properties of complex 3. The calculated vertical excitation energies in solution are consistent with the experimental data, suggesting that the transition is a metal-to-ligand charge-transfer transition. In addition, UV-vis, NMR, and cyclic voltammetry data showed that complex 3 dissociates into two mononuclear species in polar solvents: [W(CO)5(EtL)] and [W(CO)5(solvent)].

    AB - A class of dinuclear group 6 metal complexes [{M0(CO) 5}2(μ-S,S′-EtL)] (M = Cr, Mo, W) with the asymmetrically bridged zwitterionic sulfur donor bis(N,N-diethylamino) carbeniumdithiocarboxylate (EtL) was prepared by photoreaction of [M 0(CO)6] with EtL in hexane-CH2Cl2 for Cr and Mo or THF for W. The same structure in a syn-anti coordination mode was revealed by X-ray analyses for chromium(0) and tungsten(0) complexes, 1 and 3, respectively, and speculated from various analytical data for the molybdenum(0) complex 2. The pertinent criteria for the coordination mode are found to be the wavenumber of the asymmetric stretching vibration of the -CS2 moiety in the solid state and the ligand-based reduction potential in solution. Complexes 1 and 3 showed quasi-reversible reduction waves, which are assigned to a two-step, one-electron reduction process derived from the bridging EtL. In a series of [Cr(CO)5L] complexes (L = monodentate ligand), the 13C NMR chemical shifts of the trans-to-L carbonyl group showed the order of increasing σ-donor/π-acceptor ratio of the ligands. The sulfur donor ligands, including EtL and thione, are positioned in the middle of this range. All complexes exhibited negative solvatochromism: the wavelength of the absorption maximum shifted to the blue side in the range 500-600 nm with an increase in the Reichardt solvent polarity parameters ET(30), except for protic solvents. Quantum chemical calculations by time-dependent density functional theory-polarized continuum model were employed for understanding the excited states and solvatochromic properties of complex 3. The calculated vertical excitation energies in solution are consistent with the experimental data, suggesting that the transition is a metal-to-ligand charge-transfer transition. In addition, UV-vis, NMR, and cyclic voltammetry data showed that complex 3 dissociates into two mononuclear species in polar solvents: [W(CO)5(EtL)] and [W(CO)5(solvent)].

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