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Titania-supported iridium subnanoclusters as an efficient heterogeneous catalyst for direct synthesis of quinolines from nitroarenes and aliphatic alcohols

A versatile heterogeneous catalyst consisting of sub-nanosized iridium clusters deposited on titania (Ir/TiO2-NCs) promotes the direct tandem synthesis of quinoline derivatives from readily available nitroarenes and aliphatic alcohols under mild and additive-free conditions (see scheme). The process tolerates the presence of various reactive functional groups and is highly selective.

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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 of an ionic paramagnetic ruthenium(III) complex and its application as an efficient and recyclable catalyst for the transfer hydrogenation of ketones

A novel ionic complex, bis[1-butyl-2-(diphenylphosphanyl)-3- methylimidazolium]tetrachloridoruthenium(III) hexafluorophosphate (2), has been synthesized and fully characterized. The single-crystal X-ray diffraction analysis showed that 2 is composed of an Ru complex cation and PF 6- anion. The cation has a highly symmetrical Ru-centered octahedron geometry with four Cl atoms in the equatorial plane and two imidazolium-substituted phosphane ligands in the axial positions. It exhibits paramagnetism due to the presence of one unpaired electron in the phosphane-ligated low-spin RuIII complex. Complex 2 exhibited good catalytic performance in the transfer hydrogenation of a wide range of ketones by using alcohols as hydrogen donors. Owing to its high polarity, good thermal stability, and insensitivity to moisture and oxygen, complex 2 could be used in six catalytic cycles in the transfer hydrogenation of acetophenone without any obvious loss of activity. A novel ionic complex 2 containing an RuIII cation and PF6- anion has been synthesized. The Ru III cation possesses ideal octahedral geometry and exhibits paramagnetism due to the presence of one unpaired electron in the phosphane-ligated low-spin RuIII complex. Complex 2 proves to be an efficient and recyclable catalyst for the transfer hydrogenation of ketones with alcohols as hydrogen donors. 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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Asymmetric transfer hydrogenation of ketones using amino alcohol and monotosylated diamine derivatives of indane

A series of 1,2-amino alcohol and 1,2-monotosylated diamine derivatives of indane have been applied as ligands in the asymmetric ruthenium(II)-catalysed transfer hydrogenation reaction of a series of ketones. Of these, the cis-1-aminoindan-2-ol derivative gives some of the highest asymmetric inductions reported for any amino alcohol ligand in this application.

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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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Syntheses, characterization, and DFT investigation of new mononuclear acetonitrile- and chloro-ruthenium(II) terpyridine complexes

A series of mononuclear acetonitrile complexes of the type [Ru(CH3CN)(L)(terpy)]2+ {L = phen (1), dpbpy (3), and bpm (5)}, and their reference complexes [RuCl(L)(terpy)]+ {L = phen (2), dpbpy (4), and dpphen (6)} were prepared and characterized by electrospray ionization mass spectrometry, UV-vis spectroscopy, and cyclic voltammograms (CV). Abbreviations of the ligands (Ls) are phen = 1,10-phenanthroline, dpbpy = 4,4?-diphenyl-2,2?-bipyridine, bpm = 2,2?-bipyrimidine, dpphen = 4,7-diphenyl-1,10-phenanthroline, bpy = 2,2?-bipyridine, and terpy = 2,2?:6?,2?-terpyridine. The X-ray structures of the two complexes 2 and 3 were newly obtained. The metal-to-ligand charge transfer (MLCT) bands in the visible region for 1, 3, and 5 in acetonitrile were blue shifted relative to those of the reference complexes [RuCl(L)(terpy)]+. CV for all the [Ru(CH3CN)(L)(terpy)]2+ complexes showed the first oxidation wave at around 0.95 V, being more positive than those of [RuCl(L)(terpy)]+. The time-dependent-density-functional-theory approach (TDDFT) was used to interpret the absorption spectra of 1 and 2. Good agreement between computed and experimental absorption spectra was obtained. The DFT approach also revealed the orbital interactions between Ru(phen)(terpy) and CH3CN or Cl-. It is demonstrated that the HOMO-LUMO energy gap of the acetonitrile ligand is larger than that of the Cl- one.

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

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Regiocontrolled Ru-catalyzed addition of carboxylic acids to alkynes: Practical protocols for the synthesis of vinyl esters

The catalytic activity of commercially available, air and water stable ruthenium complexes in the addition of carboxylic acids to terminal alkynes was found to be drastically enhanced by the addition of small quantities of base. Moreover, the regioselectivity of the reaction can be controlled by the choice of the base so that both the Markovnikov (Na2CO3) and the anti-Markovnikov products (DMAP) are now easily accessible in excellent selectivities.

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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 of ruthenium tris(2,2?-dipyridyl) complexes containing ethynyl substituents

A method was developed for the synthesis of Ru2+ tris(2,2?-dipyridyl) complexes where one of the ligands contains substituents with triple bonds conjugated with the dipyridyl system.

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

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Method for the stereoselective synthesis of cyclic amino acids

1The instant invention is a route to stereospecific 3-substituted 5-membered ring isomers of Formula (A). The final products are useful as agents in the treatment of epilepsy, faintness attacks, hypokinesia, cranial disorders, neurodegenerative disorders, depression, anxiety, panic, pain, neuropathological disorders, gastrointestinal disorders such as irritable bowel syndrome (IBS), inflammation especially arthritis, sleep disorders, premenstrual syndrome, and hot flashes. The invention provides novel routes to synthesize stereoselectively analogs of gabapentin (Neurontin) of Formulas (I), (II), (III) and (IV) wherein R is C1-C10 alkyl or C3-C10 cycloalkyl and pharmaceutically acceptable salts thereof.

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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 the transition metal complexes: Their alcohol oxidation and electrochemical properties

Five Schiff base ligands, HA1, HA2, H 2L1-H2L3, and their Co(II), Mn(III) and Ru(III) complexes, have been synthesized and characterized by analytical, spectroscopic, conductance, magnetic moment, and electrochemical studies. The oxidation of benzylic alcohols to the corresponding carbonyl compounds is described. In the case of some primary benzyl alcohols, high conversions were obtained. Secondary benzyl alcohol (2-hydroxy-1,2-diphenylethanone derivatives) were selectively transformed to the corresponding ketone with satisfactory conversions. The electrochemical properties of all complexes have been recorded in the different scan rates and solvents. The electrochemical properties of the complexes change with scan rates. Taylor & Francis Group, LLC.

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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, Formula: Cl3Ru

Ruthenium(II) Charge-Transfer Sensitizers Containing 4,4?-Dicarboxy-2,2?-bipyridine. Synthesis, Properties, and Bonding Mode of Coordinated Thio- and Selenocyanates

The synthesis and properties of several complexes of Ru(II) containing 4,4?-dicarboxy-2,2?-bipyridine (dcbpyH2), 2,6-bis(1-methylbenzimidazol-2-yl)pyridine (bmipy), or 2,6-bis(1-methylbenzimidazol-2-yl)-4-phenylpyridine (phbmipy), and monodentate ligands (X- = Cl-, I-, NCS-, NCSe-, CN-) are reported. The introduction of the ambident ligands X- = NCS-, NCSe-, and CN- into the coordination sphere of [Ru(bmipy)(dcbpy)I]- and cis-Ru(dcbpyH2)2Cl2 has been studied in situ via 1H and 13C NMR spectroscopy using 13C-enriched ligands X-. Introduction of thiocyanate and selenocyanate initially yields the two possible linkage isomers in comparable amounts; prolonged reaction time converts the S-bound isomer and the Se-bound isomer to the N-bound isomers. The isoselenocyanate complex decomposes rapidly, yielding the cyano complex under loss of Se. The N-bound isothiocyanato complex K[Ru(bmipy)(dcbpy)(NCS)] was found to be an efficient sensitizer for nanocrystalline TiO2; the incident monochromatic photon-to-current efficiency (IPCE) is nearly quantitative at 520 nm. Introduction of a phenyl group in the 4-position of the 2,6-bis(1-methylbenzimidazol-2-yl)pyridine ligand gives a red-shifted absorption maximum for the corresponding phenylated K[Ru(ph-bmipy)(dcbpy)(NCS)] complex with an increased molar absorption coefficient for the MLCT maximum at 508 nm. At longer wavelengths above 620 nm, phenyl substitution does not enhance the absorption coefficients of the complex. Compared to that of K[Ru(bmipy)(dcbpy)(NCS)], the performance of the phenylated complex is reduced in a solar cell due to lower IPCE values. The visible spectra of the halide complexes K[Ru(bmipy)(dcbpy)X] (X- = Cl-, I-) show enhanced red response, but the complexes exhibit strongly reduced overall IPCE values. A comparison of the complexes to cis-Ru(dcbpyH2)2(NCS)2 is presented. Possible strategies for the design of more efficient sensitizers are 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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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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Reference£º
Highly efficient and robust molecular ruthenium catalysts for water oxidation,
Catalysts | Special Issue : Ruthenium Catalysts – MDPI