Novel ruthenium-oxo complexes of saturated macrocycles with nitrogen and oxygen donors and x-ray crystal structure of trans-[Ru(IV)(L)O(H2O)][ClO4]2

Ming, Chi; Tang, Wai Kit; Wong, Wing Tak; Lai, Ting Fong

doi:10.1021/ja00207a010

Cited by 89 publications

(33 citation statements)

References 1 publication

(2 reference statements)

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“…The structure consists of a Ru IV center with distorted octahedral geometry with coordinated trpy, bpy, and terminal oxido ligands. The oxido ligand displays a Ru−O bond length of 1.85 Å, which confirms its double‐bond character, as it falls within the range reported previously for related complexes . The complex crystallizes with a solvent water molecule hydrogen bonded to the oxygen atom of the Ru=O group (O oxido −O water =2.674 Å; O oxido −H=1.982 Å; O water −H=0.859 Å; O oxido −H−O water =136.59°).…”

Section: Resultssupporting

confidence: 82%

Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes

et al. 2016

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Abstract:The irreversible conversion of single-site water oxidation catalysts (WOC) into the more rugged catalysts structurally related to [(trpy)(5,5'-X2-bpy)Ru IV (µ-O)Ru IV (trpy)(O)(H2O)] 4+ (X = H, 1-dn 4+ ; X = F, 2-dn 4+ ) represents a critical issue in developing active and durable WOC. In this work, the electrochemical and acid-base properties of 1-dn 4+ and 2-dn 4+ were evaluated. In-situ resonance Raman spectroscopy was employed to characterize species formed upon stoichiometric oxidation of single-site catalysts demonstrating the formation of high oxidation states mononuclear Ru=O and RuO-O complexes. Under turnover conditions, the dinuclear intermediates, 1-dn 4+ and 2-dn 4+ , as well as the previously proposed [Ru VI (trpy)(O)2(H2O)] 2+ complex (3 2+ ) are formed. 3 2+ is a pivotal intermediate that provides access to the formation of dinuclear species. Single crystal X-ray diffraction analysis of the isolated complex [Ru IV (O)(trpy)(5,5'-F2-bpy)] 2+ reveals a clear elongation of the Ru-N bond located in the trans position to the oxo group, documenting the weakness of this bond which promotes the release of the bpy ligand and the subsequent formation of 3 2+ .

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Section: Resultssupporting

confidence: 82%

Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes

et al. 2016

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“…[42] In order to eliminate the possibility of whether Mn(II) itself takes part in the rearrangement of intermediate epoxide to PhCHO, a blank experiment was conducted using styrene oxide as the substrate. In this reaction, interestingly, aldehyde is the major product rather than the epoxide regardless of the variation in reaction conditions.…”

Section: Reprintsmentioning

confidence: 99%

Synthesis, Characterization, and Catalytic Activity of Polymer Anchored Amino Acid Mn(II) Complexes

Valodkar

Tembe

Ravindranathan

et al. 2004

Journal of Macromolecular Science, Part A

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Chloromethylated styrene-divinylbenzene copolymer beads with 6% and 8% crosslink were chemically modified by reaction with L-valine leading to the incorporation of nitrogen and oxygen as ligating sites on the surface of the polymer. These polymeric ligands on treatment with a solution of manganese(II) acetate gave the corresponding metal complex. The polymer supported Mn(II) complexes were characterized by elemental analyses, FT-IR, diffuse reflectance, ESR, scanning electron micrographs (SEM), and thermal analysis. Catalytic epoxidation of various olefins such as styrene, cis-cyclooctene, norbornylene, and cyclohexene were investigated using the supported metal complexes in presence of tert-butyl hydroperoxide as the terminal oxidant. The influence of various reaction parameters such as catalyst concentration, nature of substrate, temperature, type of oxidant, solvent etc. on conversion and selectivity was studied. Kinetic data indicate that the catalysts could be recycled without significant degradation of polymer matrix. The possible mechanistic pathways are discussed.

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“…Metal oxides are a common family of catalysts employed in various chemical processes. Ruthenium oxide molecular complexes have been used for the oxidation of water of organic molecules, and their catalytic performance has been documented in the literature. − From the fundamental point of view, there is an extensive experimental and theoretical work in the literature on the reaction of neutral and positively charged bare transition-metal oxides with either water or methane, but we are not aware of any work on the titled oxides.…”

Section: Introductionmentioning

confidence: 99%

O–H and C–H Bond Activations of Water and Methane by RuO²⁺ and (NH₃)RuO²⁺: Ground and Excited States

2019

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Investigation of the ground and excited states of RuO 2+ is carried out using multireference quantum chemical methodologies. The electronic structure is explored in detail, and accurate spectroscopic constants for 12 states are reported. Although ruthenium belongs to the same group as iron, the ground state of RuO 2+ is 1 Σ + with a strong oxo character as opposed to the 3 Δ of FeO 2+ with primarily oxyl character. To see the effect of the different electronic structure of RuO 2+ on the O−H and C−H bond activation processes, we studied its reaction with one water or methane molecule. Reaction energies and activation barriers are given for six low-lying electronic states of singlet, triplet, and quintet spin multiplicities. It is found that the higher-energy quintet state ( 5 Σ + ) provides the lowest activation energies and is the same state responsible for the C−H activation for FeO 2+ complexes. The reason is attributed to its weaker metal−oxygen bond (longer bond length), which is "prepared" to be activated at the same time with the O−H and C−H bonds. The effect of an ammonia ligand in the chemical activity is also discussed.

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Novel ruthenium-oxo complexes of saturated macrocycles with nitrogen and oxygen donors and x-ray crystal structure of trans-[Ru(IV)(L)O(H2O)][ClO4]2

Cited by 89 publications

References 1 publication

Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes

Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes

Synthesis, Characterization, and Catalytic Activity of Polymer Anchored Amino Acid Mn(II) Complexes

O–H and C–H Bond Activations of Water and Methane by RuO²⁺ and (NH₃)RuO²⁺: Ground and Excited States

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Novel ruthenium-oxo complexes of saturated macrocycles with nitrogen and oxygen donors and x-ray crystal structure of trans-[Ru(IV)(L)O(H2O)][ClO4]2

Cited by 89 publications

References 1 publication

Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes

Electrochemical and Resonance Raman Spectroscopic Studies of Water‐Oxidizing Ruthenium Terpyridyl–Bipyridyl Complexes

Synthesis, Characterization, and Catalytic Activity of Polymer Anchored Amino Acid Mn(II) Complexes

O–H and C–H Bond Activations of Water and Methane by RuO2+ and (NH3)RuO2+: Ground and Excited States

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O–H and C–H Bond Activations of Water and Methane by RuO²⁺ and (NH₃)RuO²⁺: Ground and Excited States