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The first example of Ru-catalyzed intramolecular annulation of alkynes with amides via formyl translocation has been developed, which provides an efficient approach for the synthesis of 1H-indole-3-carbaldehydes. The Royal Society of Chemistry 2012.

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

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It has been observed that the perruthenate formed on addition of ruthenium trichloride to peroxodisulphate solution in base decomposes, with loss of oxygen, to form ruthenate.Contrary to thermodynamic prediction, the latter species appears to be highly stable in the presence of excess of peroxodisulphate providing reactive organic species such as alcohols are not present.Addition of alcohols to the ruthenate-peroxodisulphate mixture at high pH affords a perruthenate-alcohol complex, the latter acting as an effective catalyst for the homogeneous oxidation of primary or secondary alcohols by the peroxodisulphate.A mechanism based on alpha-hydride abstraction has been proposed for the latter reaction, and the simultaneous formation of the insoluble dioxide RuO2*H2O attributed to further reaction of the two products, ruthenate and aldehyde.Although there have been several claims to the contrary, ruthenate (RuO42-) species do not directly oxidize alcohols (other than methanol); they are, however, capable of readily oxidizing aldehydes.

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

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The catalytic addition reactions of ferrocenyl ketones with terminal olefins in the presence of Ru(H)2(CO)(PPh3)3 as catalyst have been studied. Benzoylferrocene reacts with triethoxyvinylsilane, styrene and vinylferrocene, respectively, to give 1:1 coupling products I-III in high yields. C-H bond cleavage takes place at the carbon atom of the benzene ring at the ortho position of the carbonyl group and C-C bond formation takes place at the terminal carbon atom of the olefins. 2-Furoylferrocene reacts with vinylferrocene to give a 1:1 coupling product IV and the C-H bond cleavage takes place at the carbon atom of the furan ring at the ortho position of the carbonyl group and the C-C bond formation takes place at the terminal carbon atom of vinylferrocene. The new products I-IV have been characterized by elemental analysis, 1H-NMR and MS. The X-ray crystal structure of IV has been determined.

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

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A new series of mono and binuclear Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), La(III), Ru(III), Hf(IV), ZrO(II) and UO2(II) complexes of phenylaminodibenzoylhydrazone have been synthesized and characterized by elementals analyses, IR UV-vis spectra, magnetic moments, conductances, thermal analyses (DTA and TGA) and electron spin resonance (ESR) measurements. The IR spectral data show that, the ligand behaves as a neutral bidentate type (15 and 16), monobasic bidentate type (6), or monobasic tridentate type (5, 7, 8, 10, 11, 13, 14, 17-21) or dibasic tridentate type 2-4, 9 and 12 towards the metal ion. Molar conductances in DMF solution indicate that, the complexes are non-electrolytes. The ESR spectra of solid complexes (9 and 10) show axial and non-axial types indicating a d(x2 – y2) ground state with significant covalent bond character. However, complexes (11 and 12), show isotropic type, indicating manganese(II) octahedral geometry. Antibacterial and antifungal tests of the ligand and its metal complexes are also carried out and it has been observed that the complexes are more potent bactericides and fungicides than the ligand.

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

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A series of novel ruthenium-manganese oxide (denoted as RunMn1-nOx) has been formed by oxidative co-precipitating. The precursor was obtained by mixing Mn(VII) (potassium permanganate), Mn(II) (manganese acetate) and Ru(III) (ruthenium chloride) in neutral aqueous solution at room temperature. The powder of RunMn1-nOx was obtained by calcinating the precursor at appropriate temperature. The crystalline structure and electrochemical performance of the powder have been studied as a function of the calcination temperature. At appropriate calcination temperature (e.g. 170 C), the powder is in hydrous amorphous phase with a high specific capacitance. When the calcination temperature reaches up to 350 C, the crystal form of alpha-MnO2 is formed, but the ruthenium oxide still keeps amorphous structure, which will lead to the decrease of specific capacitance of the composite electrode materials. The X-ray photoelectron spectroscopy (XPS) analysis shows that the powder of RunMn1-nOx prepared in this study belongs to the composite of RuO2-MnO2. The results from cyclic voltammetry (CV), chronopotentiometry and electrochemical impedance spectroscopy (EIS) indicate that the ruthenium weight density of 9 wt% in RunMn1-nOx can improve the cost-performance of ruthenium-manganese composite electrode.

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

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The epoxidation of cyclic alkenes with molecular oxygen was efficiently completed in excellent epoxide yield using a novel ruthenium complex as catalyst under mild reaction conditions.

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

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Ruthenium (III) chloride catalysed oxidation of propanol-1, butanol-1, propanol-2 and butanol-2 by hexacyanoferrate (III) in sodium carbonate medium is zero order in .Rate of the reaction is directly proportional to and in the low concentration regions.After reaching a maximum value further addition of either of these retards the rate.Increase in pH of the medium retards the rate.On the basis of the results obtained a probable reaction path has been suggested.

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

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Efficient trans-hydroarylation of alkynes by simple arenes has been realized regio- and stereoselectively at room temperature in the presence of Pd(II) or Pt(II) catalysts and a mixed solvent containing trifluoroacetic acid (TFA). Various arenes undergo trans-hydroarylation selectively across terminal and internal C – C triple bonds – including those conjugated to CHO, COMe, CO2H, and CO2Et groups, affording kinetically controlled cis-arylalkenes predominantly in most cases, especially, in good yields for electron-rich arenes and activated alkynes. The formation of arene/alkyne 1/2 or 2/1 adducts as side products is dependent on the arenes’ and alkynes’ substituents, which can be suppressed in some cases by changing the catalyst, catalyst concentration, and reaction time. The Pt(II) system, PtCl2/2AgOAc/TFA, shows lower catalytic activity than Pd(OAc)2/TFA, but higher selectivity, giving higher yields of adducts at the same conversion. On the basis of several isotope experiments and control reactions, a possible mechanism involving electrophilic metalation of aromatic C – H bonds by in-situ-generated cationic Pd(II) and Pt(II) species leading to intermolecular trans-arylpalladation to alkynes has been discussed.

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

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r The title compound, [Ru(C21H21N2O 2S)Cl(C8H10O)]·CH4O or [Ru(TsDPEN)Cl(eta6-C6H5OCH2CH 3)]·CH4O [where TsDPEN is (1R,2R)-1,2-diphenyl-N- (p-toluenesulfonyl)ethylenediamine], contains an S-chiral Ru centre in a distorted octahedral environment, with similar bond lengths and angles to analogous complexes. The very short (N-)H…Cl distance of 2.61 A is ascribed to an intramolecular hydrogen bond.

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

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The (COOH)2 oxidation reaction was studied at potentials below which the oxygen evolution reaction (OER) takes place. Pt was found to catalyze the (COOH)2 oxidation reaction more strongly than Au, while Ru did not display any activity toward the (COOH)2 oxidation reaction. Furthermore, under rapid stirring conditions, the (COOH)2 oxidation reaction using Pt electrodes was shown to be activation controlled. Therefore, the (COOH)2 oxidation currents can be related to the electroactive Pt area, as shown for a range of polycrystalline, bulk metal Pt, and Pt powder electrodes. The Pt surface area for multicomponent catalyst systems can also be estimated by combining (COOH)2 oxidation data with the charge needed to oxidize adsorbed CO to CO2 (COads charge), as shown for a range of Pt- and Ru-containing powder electrodes. In fact, the combination of the two methods [(COOH)2 oxidation current and COads charge] can be used as an in situ probe to estimate the fraction of Ru in the metallic state in the potential region where CO is adsorbed provided the surface ratio of Pt vs. Ru is known.

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