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Synthesis of Ru- and Os-complexes of pi-conjugated oligomers of 2,2′- bipyridine and 5,5′-bipyrimidine. Optical properties and catalytic activity for photoevolution of H2 from aqueous media

Oligomers of 2,2′-bipyridine (Oligo-bpy) and 5,5′-bipyrimidine (Oligo- bpym) with a linear structure have been prepared by an organometallic C-C coupling reaction. The oligomeric chelating ligands have a molecular weight of about 1500 corresponding to about 10 chelating bpy or bpym units, and form soluble complexes with [M(bpy)2]2+ (M = Ru or Os). The UV-vis absorption spectra of the metal complexes of Oligo-bpy exhibit a pi-pi* transition band at 3552¡À6 nm and a peak at 453¡À18 nm assigned to a MLCT absorption. The UV- vis spectra of the metal complexes of Oligo-bpym also show an absorption peak attributed to the MLCT band. The water-soluble Ru complex of Oligo-bpy catalyzes visible-light-induced H2 evolution from aqueous media in the presence of Pt cocatalyst and triethylamine.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Application of 15746-57-3, Chemistry can be defined as the study of matter and the changes it undergoes. You¡¯ll sometimes hear it called the central science because it is the connection between physics and all the other sciences, starting with biology.15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru. In a patent, introducing its new discovery.

Photophysics and electron transfer in poly(3-octylthiophene) alternating with Ru(II)- and Os(II)-bipyridine complexes

A series of soluble metal – organic polymers that contain Ru(II) – and Os(II) – polypyridine complexes interspersed within a pi-conjugated poly(3-octylthiophene) backbone are prepared. Detailed electrochemical and photophysical studies are carried out on the polymers and two model complexes to determine the extent that the metal – polypyridine units interact with the pi-conjugated system. The results indicate that there is a strong electronic interaction between the metal-based chromophores and the pi-conjugated organic segments, and consequently the photophysical properties are not simply based on the sum of the properties of the individual components. In the Ru(II) polymers, the metal-to-ligand charge-transfer (MLCT) excited state is slightly higher in energy than the 3pi,pi* state of the poly(3-octylthiophene) backbone. This state ordering results in a material that displays only a weak MLCT luminescence and a long-lived transient absorption spectrum that is dominated by the 3pi,pi* state. In the Os(II) polymer the MLCT state is lower in energy than the polythiophene-based 3pi,pi* state and the “unperturbed” MLCT emission is observed. Finally, all of the metal-organic polymers undergo photoinduced bimolecular electron-transfer (ET) reactions with the oxidative quencher dimethyl viologen. Transient absorption spectroscopy reveals that photoinduced. ET to dimethyl viologen produces the oxidized polymers, and in most cases, the transient spectra are dominated by features characteristic of a poly(3-octylthiophene) polaron.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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High-Energy Metal to Ligand Charge-Transfer States in Ruthenium-Diimine Complexes

Earlier emission and absorption contours for the 2+ complex were anormalous.In addition, the photoselection spectra (emission and excitation) differ from that found previously for (dpy)2 complexes.Speculation was that these differences result from the high-energy metal to ligand charge-transfer (MLCT) state in this complex.Consquently, a number of bis Ru(II) chelate complexes with varying energy MLCT states were examined to rationalize these experimental results.The result with use of perturbation theory demonstrate an interaction between the singlet MLCT states and ?-?* states for these materials.The correlations of the emission Stokes shift and the zero-order energy of the singlet MLCT state indicate that singlet absorption and triplet emission derive from states of different orbital configuration.Predictions of the symmetry of the absorbing singlet and emitting triplet from a simple model are consistent with the results obtained earlier from the interchromophoric coupling model.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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10049-08-8, Name is Ruthenium(III) chloride, molecular formula is Cl3Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 10049-08-8, category: ruthenium-catalysts

Preparation, characterization and catalytic behavior of perovskites with nominal compositions La1-xSrxGa1-2yCuyRuyO3

Catalysts of the compositions La1-xSrxGa1-2yCuyRuyO3 with 0?x?0.2 and 0?y?0.35 have been prepared ex situ as powders and in situ on a cordierite monolith provided with a Ga2O3 washcoat. The samples were characterized by X-ray diffraction, scanning electron microscopy/energy dispersive spectrometry, and analytic transmission electron microscopy/energy dispersive spectrometry studies. Selected samples were subjected to catalytic tests with respect to oxidation of CO and C3H6 and reduction of NO under rich and lean conditions, respectively. It was found that Cu and Ru ions could replace Ga in the perovskite structure of LaGaO3, as outlined in the formula above, whereas the solubility of Sr was limited to x?0.10. The replacement of some Ga by Cu and Ru ions improved the catalytic activity for oxidation of CO and C3H6 and reduction of NO under rich conditions, whereas under lean conditions, no activity for reduction of NO was observed. The light-off temperatures recorded under rich conditions for oxidation of CO and C3H6 and reduction of NO for the La0.8Sr0.2Ga0.8Cu0.1Ru0.1O3 samples prepared in situ, T50 = 374, 357, and 461 C, respectively, were 50-100 lower than for the ex situ prepared sample.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Ruthenium(III) Catalyzed Oxidation of Diphenyl Sulfoxide by N-Sodio-N-Bromobenzenesulfonamide in Hydrochloric Acid: a Kinetic Study

The kinetics of oxidation of diphenylsulfoxide (DPSO) by N-sodio-N-bromobenzenesulfonamide also known as bromamine-B (BAB) has been studied in HCl solution at 30¡ãC. In the absence of Ru(III), the rate shows a first-order dependence on [BAB] and fractional-order dependence each on [DPSO] and [H(+)]. In the presence of Ru(III), the rate is firstorder with respect to [BAB] and fractional-order each on [DPSO], [H(+)] and [Ru(III)] at low acid concentration. At high acid concentration the reactionrate shows a first-order dependence each on [oxidant], [DPSO] and [H(+) ] and fractional-order on [Ru(III)]. The variation of the ionic strength, dielectric constant of the medium and addition of chloride ion and thereaction product of BAB (benzenesulfonamide) do not have any significan t effect on the reaction rate. The activation parameters have been evaluated. The value of the protonation constant of monobromamine-B, 84.7 at 303 K, is evaluated from the proposed mechanism. Mechanisms consistent with the observed kinetic data have been proposed.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Ruthenium(III)-catalyzed oxidation of 2-phenylethylamine with sodium N-chlorobenzenesulphonamide in hydrochloric acid solution: A kinetic and mechanistic study

The kinetics of ruthenium(III)-catalyzed oxidation of 2-phenylethylamine (PEA) with sodium N-chlorobenzenesulphonamide or chloramine-B (CAB) in hydrochloric acid solution has been studied at 313 K. The reaction rate shows first-order dependence each on [CAB], [H+] and [Ru(III)Cl3] and fractional order on [PEA] and [Cl-]. Variation of ionic strength and addition of the reduction product of CAB has no significant effect on the rate. There is a negative effect of dielectric constant of the solvent. The stoichiometry of the reaction was found to be 1:1 and the oxidation product of 2-phenylethylamine was identified as phenyl acetaldehyde. The reaction was studied at different temperatures and the activation parameters have been evaluated from the Arrhenius plot. The reaction constants involved in the mechanisms were computed. RN+H2Cl has been postulated as the reactive oxidizing species. Mechanisms consistent with the observed kinetic data have been proposed and discussed.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Preparation of chiral imidazolin-2-imine ligands and their application in ruthenium-catalyzed transfer hydrogenation

2-Chloro-1,3-diisopropyl-4,5-dimethylimidazolium tetrafluoroborate (1) serves as a convenient starting material for the preparation of mono- and bis(imidazolin-2-imine) ligands. Thus, the reaction of two equivalents of 1 with 1,2-ethylenediamine in the presence of potassium fluoride afforded the bis(2-aminoimidazolium) salt [BLiPrH2][BF4]2 (2), from which the achiral bis(imidazolin-2-imine) ligand N,N?-bis(1,3-diisopropyl-4,5-dimethylimidazolin-2-ylidene)-1,2-ethanediamine (BLiPr) can be obtained by deprotonation. Likewise, the reaction of 1 with (1R,2R)-(-)-1,2-diaminocyclohexane (DACH) gave [DACH(ImiPrH)2][BF4]2 (3) and its deprotonation the chiral, C2-symmetric diimine DACH(ImiPr)2 (4). Under similar conditions, chiral, C1-symmetric mono(imidazolin-2-imines) were obtained from the reaction of 1 with one equivalent of (1R,2R)-(-)-1,2-diaminocyclohexane (DACH) or (1S,2S)-(-)-1,2-diphenylethylenediamine (DPEN), which afforded the 2-aminoimidazolium salts [DACH(ImiPrH)NH2][BF4] (5) and [DPEN(ImiPrH)NH2][BF4] (6), respectively. The reaction of 4 with [(C6H6)RuCl2]2 gave ruthenium complex [(C6H6)Ru{DACH(ImiPr)2}]Cl2, [7]Cl2, which was treated with KPF6 to form [7][PF6]2. The ligand precursors 5 and 6 were deprotonated in the presence of [(C6H6)RuCl2]2, which resulted in the formation of complexes [(C6H6)Ru{DACH(ImiPr)NH2}Cl]Cl [8]Cl and [(C6H6)Ru{DPEN(ImiPr)NH2}Cl]Cl [9]Cl. Complexes [7][PF6]2, [8]Cl and [9]Cl were investigated for their ability to catalyze the transfer hydrogenation of acetophenone in isopropanol. Complex [8]Cl proved to be the most active system, while complex [9]Cl produced the highest enantioselectivity, albeit of only 27% ee. The molecular structures of [7][(C6H6)RuCl3]2¡¤CH2Cl2, formed as a side product, and of [8]Cl¡¤acetone were determined by X-ray diffraction analyses.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru. In a Article£¬once mentioned of 15746-57-3, category: ruthenium-catalysts

Reversible hydride generation and release from the ligand of [Ru(pbn)(bpy)2](PF6)2 driven by a pbn-localized redox reaction

(Chemical Equation Presented) Electrochemical reduction of [Ru(pbn)-(bpy)2]2+ (1, pbn = 2-(2-pyridyl)benzo[b]-1,5- naphthyridine, bpy = 2,2?-bipyridine) in an acidic solvent gives [Ru(pbnH2)-(bpy)2]2+ (2), which releases the hydrogen as “hydride” (see scheme). This catalytic system reduces substrates (for example, acetone) with two electrons and protons from water, and thus operates in a similar way to the NAD+/NADH redox couple.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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In an article, published in an article, once mentioned the application of 14564-35-3, Name is Dichlorodicarbonylbis(triphenylphosphine)ruthenium(II),molecular formula is C38H34Cl2O2P2Ru, is a conventional compound. this article was the specific content is as follows.category: ruthenium-catalysts

Conversion of Coordinated Carbon Monoxide into Carbon Dioxide via Oxygen-atom transfer from Coordinated Nitrite: Thermolysis of Ru(NO2)2(CO)2(PPh3)2

The thermolysis (111 deg C, toluene solution) of Ru(NO2)2(CO)2(PPh3)2 in the presence of excess PPh3 procced according to the stoichiometry Ru(NO2)2(CO)2(PPh3)2 + PPh3 -> Ru(NO2)2(PPh3)2 + CO2 + CO + Ph3PO.Two highly selective oxygen-atom transfer processes are involved in the overall thermolysis reaction: (i) Ru(NO2)2(CO)2(PPh3)2 -> Ru(ONO)(CO)(NO)(PPh3)2 + CO2; (ii) Ru(ONO)(CO)(NO)(PPh3)2 + PPh3 -> Ru(NO2)2(PPh3)2 + CO + Ph3PO.The intermediate complex Ru(ONO)(CO)(NO)(PPh3)2 was synthesized independently and has been characterized by analytical and spectral methods.The thermolysis of Ru(N18O2)2(CO)2(PPh3)2 unambiguosly establishes coordinated NO2- as the source of oxygen in the conversion of coordinated CO into CO2.Moreover, the extent of 18O enrichment in the CO2 product indicates that statistical scrambling of oxygen occurs between nitrogen and carbon atoms prior to the loss of CO2.The results of a double-label study involving the thermolysis of Ru(N18O2)2(CO)2(PPh3)2 and Ru(NO2)2(13CO2)2 are consistent with an intermolecular mechanism for oxygen-atom transfer from NO2- to CO.Additional mechanistic implications are described.

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Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI

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Synthesis and characterization of novel oxime-imine ligands and their heteronuclear ruthenium(III) complexes

Vicinal carbonyl oxime (HL1) and oxime-imine (H 2L2) ligands and their mononuclear Ru(III) and Cu(II), heterodinuclear Ru(III)-Mn(II), Ru(III)-Ni(II), Ru(III)-Cu(II), and heterotrinuclear Ru(III)-Cu(II)-Ru(III) chelates were synthesized and characterized by elemental analysis, molar conductivity, IR, ESR, ICP-OES, magnetic moment measurements, and thermal analyses studies. The free ligands were also characterized by 1H NMR spectra. The carbonyl-oxime ligand coordinates through the oxygen of =N-OH to form a six-membered chelate ring. The quadridentate tetraaza ligand (H2L2) obtained by condensing of the bidentate ligand 1-p-diphenylmethane-2-hydroxyimino-2-(1- naphthylamino)-1-ethanone (HL1) with 1,2-phenylenediamine coordinates with Ru(III) through its nitrogen donors in the equatorial position with the loss of one of the oxime protons and concomitant formation of an intramolecular hydrogen bond. Stoichiometric and spectral results of the metal complexes indicated that the metal: ligand ratios in the mononuclear complexes of the ligand (HL1) were found to be 1: 2, while these ratios were 1: 1 in the mononuclear complexes of the ligand (H2L2). The metal: ligand ratios of the dinuclear complexes were found to be 2: 1, and this ratio was 3: 2 in the trinuclear complex.

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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI