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Ruthenium(III) catalysed oxidation of gabapentin (neurontin) by diperiodatonickelate(IV) in aqueous alkaline medium: A kinetic and mechanistic study

The kinetics of Ru(III) catalysed oxidation of neuroleptic drug, gabapentin by diperiodatonickelate(IV) (DPN) in alkaline medium at 298 K and a constant ionic strength of 0.30 mol dm-3 was studied spectrophotometrically. The oxidation products are 1-(hydroxymethyl) cyclohexane acetic acid and Ni(II) which are identified by spectral studies. The stoichiometry of the reaction is 1:1 which is similar as in the case of absence of ruthenium(III). The oxidation reaction in alkaline medium has been shown to proceed via a Ru(III)-gabapentin complex, which further reacts with deprotonated form of DPN in a rate determining step, which is followed by other fast steps to give the products. The reaction constants involved in the different steps of the mechanism are calculated. The activation parameters with respect to slow step of the mechanism are computed and discussed and thermodynamic quantities are also determined. The catalytic constant (KC) was calculated at different temperatures. The probable active species of catalyst and oxidant have been identified.

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

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Effect of support type and synthesis conditions on the oxygen reduction activity of RuxSey catalyst prepared by the microwave polyol method

RuxSey nanoparticles supported on different carbon substrates were synthesized by microwave heating of ethylene glycol solutions of Ru(III) chloride and sodium selenite at different pH and Ru/Se mole ratios. The resulting catalysts were used for the electrochemical oxygen reduction reaction (ORR) in acidic solution. The electrochemical activity was highest for the supported catalyst synthesized at pH 8. Increasing the Se concentration of the catalyst up to 15 mol% increased the catalytic activity for the ORR; at this Se concentration, the activity of the catalyst was considerably higher than that observed for pure Ru catalyst synthesized at exactly the same conditions. The influence of the type of carbon support on the activity of the electrocatalyst was also investigated. Among the different supports, including carbon black (Vulcan XC-72R) (C1), and nanoporous carbons synthesized from resorcinol- (C2) and phloroglucinol-formaldehyde (C3) resins, the RuxSey catalyst supported on C3 exhibited highest activity for ORR.

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

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alpha-Alkylation of carbonyl compounds by direct addition of alcohols to Enol acetates

A practical alpha-alkylation of ketones and aldehydes has been achieved by the direct addition of alcohols to enol acetates. The moderate Lewis acidity of InI3, CaBr3, and FeBr3 is a key factor in the catalytic cycle, and many different alcohols and enol acetates have been successfully used in this procedure.

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

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Fully delocalized (ethynyl)(vinyl)phenylene bridged triruthenium complexes in up to five different oxidation states

Triruthenium [(dppe)2Ru{-C-muC-1,4-C6H 2-2,5-R2-CH=CH-RuCl(CO)(PiPr3) 2}2]n+ (4a, R = H; 4b, R = OMe) containing unsymmetrical (ethynyl)(vinyl)phenylene bridging ligands and displaying five well-separated redox states (n = 0-4) are compared to their bis(alkynyl) ruthenium precursors (dppe)2Ru{-C-muC-1,4-C6H 2-2,5-R2-C-muCR?} (2a,b: R? = TMS; 3a,b: R? = H) and their symmetrically substituted bimetallic congeners, complexes {Cl(dppe)2Ru}2{mu-C-muC-1,4-C 6H2-2,5-R2-C-muC} (Aa, R = H; Ab, R = OMe) and {RuCl(CO)(PiPr3) 2}2{mu-CH=CH-1,4-C6H2-2,5-R 2-CH=CH} (Va, R = H; Vb, R = OMe) as well as the mixed (ethynyl)(vinyl)phenylene bridged [Cl(dppe)2Ru-C-muC-1,4- C6H4-CH=CH-RuCl(CO)(PiPr3) 2] (Ma). Successive one-electron transfer steps were studied by means of cyclic voltammetry, EPR and UV-vis-NIR-IR spectroelectrochemistry. These studies show that the first oxidation mainly involves the central bis(alkynyl) ruthenium moiety with only limited effects on the appended vinyl ruthenium moieties. The second to fourth oxidations (n = 2, 3, 4) involve the entire carbon-rich conjugated path of the molecule with an increased charge uniformly distributed between the two arms of the molecules, including the terminal vinyl ruthenium sites. In order to assess the charge distribution, we judiciously use 13CO labeled analogues to distinguish stretching vibrations due to the acetylide triple bonds and the intense and charge-sensitive Ru(CO) IR probe in different oxidation states. The comparison between complex pairs 4a,bn+ (n = 0-3), A a,bn+ and Va,bn+ (n = 0-2) serves to elucidate the effect of the methoxy donor substituents on the redox and spectroscopic properties of these systems in their various oxidation states and on the metal/ligand contributions to their frontier orbitals.

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

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Vapour pressure and thermoanalytical study of diethyldithiocarbamates of platinum metals

A thermoanalytical study of the diethyldithiocarbamates of the platinum metals Pt(II), Pd(II), Rh(III), Ir(III) and Ru(III) was carried out by means of DTA techniques in an inert atmosphere and in vacuum. Decomposition temperatures were determined and the mass loss curves were obtained for these compounds in helium and in vacuum. The X-ray diffraction patterns of the solid products of M(dtk)n thermolysis were studied. The temperature dependences of the saturated vapour pressures of the listed chelates were measured by flow and Knudsen methods, and the vaporization parameters were determined.

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Reference£º
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. 10049-08-8, Name is Ruthenium(III) chloride, molecular formula is Cl3Ru. In a Article£¬once mentioned of 10049-08-8, name: Ruthenium(III) chloride

Ubiquitous strategy for probing ATR surface-enhanced infrared absorption At platinum group metal-electrolyte interfaces

A versatile two-step wet process to fabricate Pt, Pd, Rh, and Ru nanoparticle films (simplified as nanofilms hereafter) for in situ attenuated total reflection Fourier transform infrared (ATR-FTIR) study of electrochemical interfaces is presented, which incorporates an initial chemical deposition of a gold nanofilm on the basal plane of a silicon prism with the subsequent electrodepostion of desired platinum group metal overlayers. Galvanostatic electrodeposition of Pt, Rh, and Pd from phosphate or perchloric acid electrolytes, or potentiostatic electrodeposition of Ru from a sulfuric acid electrolyte, yields sufficiently “pinhole-free” overlayers as evidenced by electrochemical and spectroscopic characterizations. The Pt group metal nanofilms thus obtained exhibit strongly enhanced IR absorption. In contrast to the corresponding metal films electrochemically deposited directly on glassy carbon and bulk metal electrodes, the observed enhanced absorption for the probe molecule CO exhibits normal unipolar band shapes. Scanning tunneling microscopic (STM) images reveal that fine nanoparticles of Pt group metals are deposited around wavy and stepped bunches of Au nanoparticles of relatively large sizes. This ubiquitous strategy is expected to open a wide avenue for extending ATR surface-enhanced IR absorption spectroscopy to explore molecular adsorption and reactions on technologically important transition metals, as exemplified by successful real-time spectroscopic and electrochemical monitoring of the oxidation of CO at Pd and that of methanol at Pt nanofilm electrodes. The spectral features of free water molecules coadsorbed with CO on Pt, Pd, Rh, and Ru are also discussed. A 2005 American Chemical Society.

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

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Effect of the anchoring group (carboxylate vs phosphonate) in Ru-complex-sensitized TiO2 on hydrogen production under visible light

We synthesized six Ru-bipyridyl complexes having di-, tetra-, and hexacarboxylate (C2, C4, and C6) and di-, tetra-, and hexaphosphonate (P2, P4, and P6) as the anchoring group, prepared six different sensitized TiO 2 samples by using them, and then systematically tested their visible light reactivity for hydrogen production in aqueous suspension (with EDTA as an electron donor) under lambda > 420 nm illumination. The properties and efficiencies of C- and P-complexes as a sensitizer depended on the number and kind of anchoring groups in very different ways. The adsorption of P-complexes on TiO2 is strong enough not to be hampered by the presence of competing adsorbates (EDTA), whereas that of C-complexes is significantly inhibited. As a result, P – TiO2 exhibited much higher activity for the hydrogen production than C – TiO2, although the visible light absorbing capabilities are comparable among C- and P-complexes. Among the six sensitizers, P2 was the most active one for the H2 production. The hydrogen production activities of C – TiO2 and P – TiO2 depended on the concentration of sensitizers and electron donors in different ways as well. How the sensitizing activity for hydrogen production is influenced by the anchoring group and the experimental conditions was investigated and discussed in detail. It is also notable that the effects of the anchoring group on the sensitized production of hydrogen were drastically different from those on the dye-sensitized solar cell we recently reported for the same set of six sensitizers.

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

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Biomimetic syntheses from squalene-like precursors: Synthesis of ent- abudinol B and reassessment of the structure of muzitone

We achieved the stereoselective syntheses of two different structural patterns corresponding to the enantiomers of the marine natural products abudinol B and muzitone, by developing two-directional tandem biomimetic cyclizations of polyepoxides of squalene analogues in which one alkene was functionalized as an enolsilane. In the course of this work, we demonstrated that the structure of muzitone was misassigned.

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

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Dependence of CH3OH oxidation activity for a wide range of PtRu alloys detailed analysis and new views

Unsupported PtRu alloy powders of a wide range of compositions were prepared at low temperatures by carefully adjusting the preparation procedure. PtRu alloys of essentially the same surface, nominal and bulk composition, were formed up to ca. 46 atom % Ru content. Adsorbed CO stripping voltammetry and CH3OH oxidation characteristics, namely, i-V curves and pseudo-steady-state current density values recorded at constant potentials, were the same as reported for corresponding bulk alloys, suggesting that the electrocatalytic activities of the powders can be compared to bulk alloys. CH3OH oxidation activities obtained for PtRu alloy, Pt, and Ru powders showed the PtRu alloy of 70:30 atom % Pt:Ru composition to exhibit the highest activity independent of the temperature and potential tested (0.3 and 0.4 V vs. a reversible hydrogen electrode). The experimental pseudo-steady-state current density values for the CH3OH oxidation reaction were found to show the same dependence on Ru content as theoretical values calculated assuming that an assembly of three neighboring Pt and one Ru site are involved in the oxidation of a CH3OH molecule.

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

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Simple replacement reaction for the preparation of ternary Fe 1-xPtRux nanocrystals with superior catalytic activity in methanol oxidation reaction

The finding of new metal alloyed nanocrystals (NCs) with high catalytic activity and low cost to replace PtRu NCs is a critical step toward the commercialization of fuel cells. In this work, a simple cation replacement reaction was utilized to synthesize a new type of ternary Fe 1-xPtRux NCs from binary FePt NCs. The detailed structural transformation from binary FePt NCs to ternary Fe1-xPtRux NCs was analyzed by X-ray absorption spectroscopy (XAS). Ternary Fe 35Pt40Ru25, Fe31Pt 40Ru29, and Fe17Pt40Ru43 NCs exhibit superior catalytic ability to withstand CO poisoning in methanol oxidation reaction (MOR) than do binary NCs (FePt and J-M PtRu). Also, the Fe31Pt40Ru29 NCs had the highest alloying extent and the lowest onset potential among the ternary NCs. Furthermore, the origin for the superior CO resistance of ternary Fe1-xPtRu x NCs was investigated by determining the adsorption energy of CO on the NCs surfaces and the charge transfer from Fe/Ru to Pt using a simulation based on density functional theory. The simulation results suggested that by introducing a new metal into binary PtRu/PtFe NCs, the anti-CO poisoning ability of ternary Fe1-xPtRux NCs was greatly enhanced because the bonding of CO-Pt on the NCs surface was weakened. Overall, our experimental and simulation results have indicated a simple route for the discovery of new metal alloyed catalysts with superior anti-CO poisoning ability and low usage of Pt and Ru for fuel cell applications.

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