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Metal complexes of the type ML2Cl2 and M?2L2Cl6 where M = Mn(II), Co(II), Ni(II) and Cu(II), M? = Ru(III) or Rh(III) and L = 2-(1-indazolyl)benzothiazole have been prepared and characterized. The IR spectra reveal that the ligand is bidentate coordinating through the N-atoms of both the indazole and benzothiazole groups. Magnetic susceptibility measurements and the electronic spectral data suggest a six-coordinated octahedral structures for these complexes.

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

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The conformational properties of a series of iron(II) and ruthenium(II) tris-bipyridine complexes have been investigated in a range of solvents. The complexes are equipped with pendant aromatic esters attached by flexible aliphatic linkers, and aromatic interactions between the edge of the bipyridine units and the face of the aromatic esters cause the complexes to fold up in solution. The extent of folding is assessed using 1H chemical shifts and found to be strongly solvent-dependent. Strong intramolecular edge-to-face aromatic interactions leading to stable folded structures are found in both polar solvents (water and alcohols) and nonpolar solvents (chlorinated hydrocarbons), but solvents of intermediate polarity such as DMSO destabilize the folded conformation. These results indicate that the aromatic interactions are dominated by a substantial electrostatic contribution in organic solvents but are sufficiently nonpolar to take advantage of solvophobic effects in polar solvents. This solvent dependence is likely to be a characteristic feature of any molecular recognition process which involves a mixture of both polar and nonpolar interactions.

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

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1-En-6-ynes react with alcohols or water in the presence of PtCl2 as catalyst to give carbocycles with alkoxy or hydroxy functional groups at the side chain. The reaction proceeds by anti attack of the alkene onto the (eta2-alkyne)platinum complex. The formation of the C – C and C – O bonds takes place stereoselectively by trans addition of the electrophile derived from the alkyne and the nucleophile to the double bond of the enyne. Formation of five- or six-membered carbo- or heterocycles could be obtained from 1-en-6-ynes depending on the substituents on the alkene or at the tether. Although more limited in scope, Ru(II) and Au(III) chlorides also give rise to alkoxy- or hydroxycyclization of enynes. On the basis of density functional theory (DFT) calculations, a cyclopropyl platinacarbene complex was found as the key intermediate in the process. In the presence of polar, nonnucleophilic solvents, 1-en-6-ynes are cycloisomerized with PtCl2 as catalyst. Formation of a platinacyclopentene intermediate is supported by DFT calculations. The reaction takes place by selective hydrogen abstraction of the trans-allylic substituent. Cycloisomerization of enynes containing disubstituted alkenes could be carried out using RuCl3 or Ru(AsPh3)4Cl2 in MeOH.

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

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The synthesis of an optically pure proline-based tryptophan mimetic is described. The strategy involves the in situ generation of an unprecedented allylmetal species containing the indole moiety, and its coupling with a chiral imine. The construction of the 3-substitued proline skeleton is then achieved through a hydrozirconation/iodination sequence applied to the resulting homoallylic amine.

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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 structurally characterized mixed-valent tetranuclear ruthenium-oxo oxalato cluster exhibits anti-viral activities toward R5- and X4-tropic HIV-1, and possesses cytoprotective activity toward HIV-1 infected cells. Copyright

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

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The charge storage mechanism of nanostructured anhydrous and hydrous ruthenium-based oxides was evaluated by various electrochemical techniques (cyclic voltammety, hydrodynamic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy). The effects of various factors, such as particle size, hydrous state, and structure, on the pseudocapacitive property were characterized. The electric double layer capacitance (Cdl), adsorption related charge (Cad), and the irreversible redox related charge (Cirr) per unit mass and surface area of electrode material has been estimated and the role of structural water within the material either in micropores or interlayer are discussed.

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

Extended knowledge of Ruthenium(III) chloride

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A facile and flexible approach for the preparation of Ru(ii) complexes containing different carbohydrates based on the Cu(ii)-catalyzed Huisgen-[3+2] cycloaddition is described.

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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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Diffusion pairs of RuO2 and glass were prepared as model specimens for composite thick-film resistors and chemical and electrical microanalyses were carried out at the interface to clarify the piezoresistive mechanism of the resistors. The diffusion of ruthenium into glass was examined with SIMS and the chemical structure was analyzed with EELS. In situ measurement of resistance change was conducted as a function of applied load with a microprobe on the RuO2-glass interfaces locally by conductive AFM. The glass with higher piezoresistive sensitivity was found to have larger amount of diffused ruthenium, which has trivalent and tetravalent states in the glass. The originally insulative glass showed electrical conductivity by the diffusion of ruthenium. Furthermore, load-dependent conductivity change was observed near the interface. The analysis suggests that the conduction mechanism is variable range hopping and that the strain-derived electronic state changes must be the origin of the piezoresistive effect of the thick film resistors.

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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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We demonstrate a new solid-state synthesis route to prepare calcium borohydride, Ca(BH4)2 by reacting a ball-milled mixture of CaB6 and CaH2 in a molar ratio of 1:2 at 700 bar of H2 pressure and 400-440C. Moreover, doping with catalysts was found to be crucial to enhance reaction kinetics. Thermogravimetric analysis and differential scanning calorimetry revealed a reversible low-temperature to high-temperature endothermic phase transition at 140C and another endothermic phase transition at 350-390C associated with hydrogen release upon formation of CaB6 and CaH2, as was evident from X-ray diffraction analysis. Thus, since Ca(BH4)2 here is shown to be prepared from its anticipated decomposition products, the conclusion is that it has potential to be utilized as a reversible hydrogen storage material. The theoretical reversible capacity was 9.6 wt % hydrogen.

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

Discovery of Ruthenium(III) chloride

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We report the first investigation of ruthenium electrodeposition on Au(1 1 1) from an ionic liquid, 1-butyl-3-methylimidazolium dicyanamide, which exhibits sufficient solubility of RuCl3 at room temperature. Employing cyclic voltammetry and in situ electrochemical scanning tunneling microscopy (EC-STM) we find that Ru(IV)-complex formation is a necessary prerequisite for Ru metal deposition from this ionic liquid. The corresponding oxidation reaction occurs at an anodic potential of ?0.6 V vs. Pt/Pt(II). Thin Ru films of ?5 nm average thickness and with a relatively homogeneous morphology have been grown with a very slow growth rate of 0.1 nm min-1. The metallic nature of these films is proven by X-ray photoelectron spectroscopy.

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