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CATALYSIS OF HYDROSILYLATION. VII. CATALYSIS OF HYDROSILYLATION OF C=C BONDS BY RUTHENIUM PHOSPHINE COMPLEXES

A full account of the catalysis of hydrosilylation of the C=C bond in olefins, their derivatives with functional groups as well as in vinyl-trisubstituted silanes by ruthenium(II) and ruthenium(III) phosphine precursors is given.The ruthenium complexes are far more efficient catalysts for the hydrosilylation of 1-alkenes and vinyl-substituted silanes than for the substituted olefins and unsaturated esters.General features characterizing all hydrosilylation reactions catalyzed by the above catalysts are as follows: the reaction proceeds with alkoxy-substituted silanes(also with vinylsilanes) in the absence of solvent, and is enhanced (for RuII and olefins occurs exclusively) in the presence of molecular oxygen.Two general mechanisms are proposed for hydrosilylation of olefins and of vinylsilanes, respectively, which account for most of the experimental observations.

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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. 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, Product Details of 15746-57-3

Observation of cascade f ? d ? f energy transfer in sensitizing near-infrared (NIR) lanthanide complexes containing the Ru(ii) polypyridine metalloligand

Distinguishable d ? f or f ? d energy transfer processes depending on lanthanide ions are observed in isomorphous d-f heterometallic complexes containing the Ru(ii) metalloligand (LRu), which lead to sensitized NIR emission (for Nd3+ and Yb3+) or enhanced red emission of LRu (for Eu3+ and Tb3+), and represent the first eye-detectable evidence of f ? d energy transfer processes in Ln-Ru bimetallic complexes. Based on the systematic luminescence and decay lifetime study, cascade f ? d ? f energy transfer has been proposed in Ln1-Ru-Ln2 trimetallic systems for improved NIR sensitization.

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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. 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2. In a Article£¬once mentioned of 37366-09-9, Recommanded Product: 37366-09-9

The enantioselective synthesis of (S)-(+)-mianserin and (S)-(+)-epinastine

A simple enantioselective synthetic procedure for the preparation of mianserin and epinastine in optically pure form is described. The key step in the synthetic pathway is the asymmetric reduction of the cyclic imine using asymmetric transfer hydrogenation conditions.

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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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Preparation and Redox Behavior of a Series of Mixed Ligand Cp*/ aqua/tripod Complexes of Co, Rh and Ru

The following series of complexes n+ was prepared: M = Co, Rh, Ru, a) L,L’= eta5-C5Me5, b) L,L’ = eta5-C5Me5, H2O, c) L,L’ = eta5-C5Me5, tripod (CpCo(P(O)(OEt)2)3-), d) L,L’ = tripod.Redox transitions of the complexes were investigated by cyclic voltammetry.The results are discussed in therms of ligand field and ligand charge stabilization of the respective electron configurations.

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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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Chiral salicyloxazolines as auxiliaries for the asymmetric synthesis of ruthenium polypyridyl complexes

Chiral auxiliaries are promising emerging tools for the asymmetric synthesis of octahedral metal complexes. We recently introduced chiral salicyloxazolines as coordinating bidentate chiral ligands which provide excellent control over the metal-centered configuration in the course of ligand substitution reactions and can be removed afterward in an acid-induced fashion under complete retention of configuration (J. Am. Chem. Soc. 2009, 131, 9602-9603). Here reported is our detailed investigation of this sequence of reactions, affording virtually enantiopure ruthenium polypyridyl complexes. The control of the metal-centered chirality by the coordinated chiral salicyloxazolinate ligand was evaluated as a function of reaction conditions, the employed bidentate 2,2?-bipyridine and 1,10-phenanthroline ligands, and the substituent at the asymmetric 5-position of the oxazoline heterocycle. Most striking was the strong influence of the reaction solvent, with aprotic solvents of lower polarity providing the most favorable diastereoselectivities. Through a combination of computational and experimental results, it was revealed that the observed stereoselectivities are under thermodynamic control. The removal of the chiral salicyloxazoline auxiliary under retention of the configuration requires acidic conditions and a coordinating solvent such as MeCN or THF in order to prevent partial racemization. This method represents the first general strategy for the asymmetric synthesis of enantiopure heteroleptic ruthenium polypyridyl complexes.

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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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Studies in kinetics and mechanism of oxidation of d-glucose and d-fructose by alkaline solution of potassium iodate in the presence of Ru(III) as homogeneous catalyst

Kinetics of oxidation of d-glucose (glc) and d-fructose (fru) by potassium iodate has been studied for the first time in alkaline medium using Ru(III) as homogeneous catalyst. The linear dependence of the reaction rate at lower [IO3-] and [OH-] tends towards zero-order at their higher concentrations. Experimental results also show that the order with respect to [Ru(III)] is unity and the order with respect to [reducing sugar] is zero in the oxidation of both glc and fru. Variation in [Cl-] and ionic strength (mu) of the medium does not affect the oxidation rate. The species, [RuCl2(H2O)2(OH)2]- and IO3-, were found to be the reactive species of Ru(III) chloride and potassium iodate in alkaline medium, respectively. The reactions have also been studied at four different temperatures and with the help of observed values of pseudo-first-order rate constant (k1), the entropy of activation and other activation parameters have been calculated. A common mechanism, where the rate determining step involves the interaction between reactive species of Ru(III) chloride and reactive species of potassium iodate resulting in the formation of an activated complex,{A figure is presented}has been proposed. The formation of activated complex is very well supported by the spectrophotometric evidence, observed kinetic data and also by the negative entropy of activation observed for the oxidation of both glc and fru. Arabinonic acid and formic acid were identified as the main oxidation products of the reactions.

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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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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Article£¬once mentioned of 301224-40-8, HPLC of Formula: C31H38Cl2N2ORu

Enantioselective total synthesis of pinnaic acid and halichlorine

The enantioselective total synthesis of the bioactive marine natural products pinnaic acid and halichlorine is reported in detail. Our total synthesis features the construction of the five-membered ring and C9 and C13 stereogenic centers through a palladium-catalyzed trimethylenemethane [3+2] cyclization; the installation of the nitrogen atom through a regioselective Beckmann rearrangement of a poorly reactive ketone; the stereoselective cyclization of the spiro ring through a four-step, one-pot hydrogenation- cyclization; and efficient connection of the sterically hindered lower chain through a reduced-pressure cross olefin metathesis reaction. Copyright

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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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Surface and electrochemical characterization of electrodeposited PtRu alloys

PtRu alloys of different compositions were electrodeposited on Au. Twelve alloys between 0% and 100% Pt were characterized with surface sensitive spectroscopies (XPS, LEIS) after transfer from an electrochemical cell to an ultra high vacuum chamber without contact to air. The composition of the thus prepared alloys showed a linear dependence on the concentrations of the deposition solution, but was Pt-enriched both in the bulk and (even more so) at the surface. During the electrochemical reduction of the metal cations, sulfur from the supporting electrolyte 1N H2SO4 was found to be incorporated into the electrodes. Cyclic voltammetry was used for the determination of the electrocatalytic activity of the electrodes for the oxidation of carbon monoxide. The highest activity for this oxidation as measured by the (peak) potential of the CO oxidation cyclovoltammograms was found for a surface concentration of approx. 50% Pt. The asymmetry of this ‘activity curve’ (oxidation potential versus Pt surface concentration) is tentatively explained in terms of a surface structural phase separation.

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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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Targeting nucleus DNA with a cyclometalated dipyridophenazineruthenium(II) complex

Recently, coordinatively saturated and substitutionally inert Ru(II) complexes have been investigated as anticancer agents. Herein a cyclometalated Ru(II) complex, [Ru(bpy)(phpy)(dppz)]+, was found to be rapidly taken up by cancer cells, and nearly 90% of the complex accumulated in the nuclei of cancer cells after a 2 h incubation. The anticancer activity of this complex was screened against a panel of cancer cell lines. Remarkably, it exhibited IC50 values that were an order of magnitude lower than those of cisplatin. This complex also displayed potencies superior to those of cisplatin against 3D tumor spheroids. Further studies revealed that the high DNA binding affinity of [Ru(bpy)(phpy)(dppz)]+ resulted in effective disruption of the binding of transcription factor NF-kappaB to DNA sequences, thereby inhibiting cellular transcription and leading to irreversible cancer cell apoptosis. Our work provides new insights into understanding the biological interactions and anticancer molecular mechanisms of DNA-specific Ru(II) polypyridyl complexes.

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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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Caged amino acids for visible-light photodelivery

We present a photocleavable protecting group based on ruthenium bipyridyl complexes and suitable for amino acid photodelivery. We discuss the photochemical properties of the caged glutamate, which is a major neurotransmitter in the CNS. The molar absorptivity for the caged glutamate at 450 nm is epsilon = 4200 M-1cm-1 and its quantum yield of photore-lease at 450 nm is ?PD = 0.035, which is about 17 times higher than that of the most active organic caged compound at this wavelength. Similar figures are obtained for other ?-amino acids. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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