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Chemical and light-driven oxidation of water catalyzed by an efficient dinuclear ruthenium complex

Here splits the sun: A dinuclear ruthenium complex has been synthesized and employed to catalyze the homogeneous water oxidation (see picture; purple Ru, green Cl, blue N, red O). An exceptionally high turnover number was observed both for chemical (CeIV as the oxidant) and light-driven ([Ru(bpy)3]2+-type photosensitizers) water splitting.

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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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Kinetics and Mechanism of Ruthenium(III) Catalysed Oxidation of Benzylamine by Hexacyanoferrate(III) in Alkaline Medium

The kinetics of ruthenium(III) catalysed oxidation of benzylamine by potassium hexacyanoferrate(III) in alkaline medium has been carried out.The reaction has been observed to be zero order with respect to oxidant and first order to lower concentrations of substrate and alkali tending towards zero order at their higher concentrations.Further, with respect to ruthenium(III), the order has been observed to be unity.A probable mechanism explaining all the observed results has been postulated.The activation parameters have been calculated.

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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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KINETICS AND MECHANISM OF RUTHENIUM(III)-CATALYSED OXIDATION OF ALLYL ALCOHOL BY MOLECULAR OXYGEN.

Oxidation of allyl alcohol by molecular oxygen catalysed by ruthenium(III) chloride in the pH range 1. 0 – 3. 0 is reported. The kinetics of the reaction, in the pH range 1. 0 – 2. 0, indicate a first-order dependence on ruthenium(III) ion and allyl alcohol concentrations and a zero-order dependence with respect to molecular oxygen concentration. The rate of oxidation was also found to be directly proportional to the hydrogen ion concentration. In the pH range 2. 0 – 3. 0, the rate of oxidation of allyl alcohol was found to be first order with respect to ruthenium(III) ion, first order with respect to allyl alcohol, and inversely proportional to hydrogen ion concentration.

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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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Electronic and geometrical manipulation of the excited state of bis-terdentate homo- and heteroleptic ruthenium complexes

This work describes the synthesis and characterization of two new bis-terdentate Ru(ii) complexes. Compound 1 is a homoleptic complex containing two CNC N-heterocyclic carbene (NHC) based ligands, whereas compound 2 bears one CNC ligand and an ancillary terpyridine ligand. The redox and photophysical properties of both compounds have been investigated and their X-ray crystal structures determined. Complex 1 displays a close-to-perfect octahedral coordination geometry and is not luminescent at room temperature while complex 2 features room temperature and 77 K luminescence despite its partially distorted geometry. The presence of the NHC moieties brings a significant amount of electronic density to the metal centre therefore lowering its oxidation potential with respect to that of analogous polypyridyl complexes. The Royal Society of Chemistry 2011.

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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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Water-soluble hydroxyalkylated phosphines: Examples of their differing behaviour toward ruthenium and rhodium

The reaction of P(CH2OH)3 (I) and P(C 6H5)(CH2OH)2 (II) with RuCl 3 in methanol eliminates two equivalents of formaldehyde to yield the mixed tertiary and secondary phosphine complexes all-trans-[RuCl 2(P(CH2OH)3)2 (P(CH 2OH)2H)2] (1) and [RuCl2(P(C 6H5)(CH2OH)2)2(P(C 6H5)(CH2OH)H)2] (2), respectively. There is a high degree of hydrogen-bonding interactions between the hydroxymethyl groups in 1 and 2, although the phenyl groups of the latter reduce the extent of the network compared to 1. The generation of these mixed secondary and tertiary phosphine complexes is unprecedented. Under the same reaction conditions, the tris(hydroxypropyl)phosphine III formed no ruthenium complex. The reaction of P(CH2OH)3, P(C6H 5)(CH2OH)2 and P{(CH2) 3OH}3 with [RhCl(1,5-cod)]2 in an aqueous/dichloromethane biphasic medium yielded [RhH2(P(CH 2OH)3)4]+ (3), [RhH 2(P(C6H5)(CH2OH)2) 4]+, (4) and [Rh(P(C6H5)(CH 2OH)2)4]+ (5) and [Rh(P{(CH 2)3OH}3)4]+ (6), respectively. Treating 5 with dihydrogen rapidly gave 4. The hydroxypropyl compound 6 formed the corresponding dihydride much more slowly in aqueous solution, although [RhH2(P{(CH2)3OH} 3)4]+ (7) was readily formed by reaction with dihydrogen. Two separate reaction pathways are therefore involved; for P(CH 2OH)3 and to a lesser extent P(C6H 5)(CH2OH)2, the hydride source in the product is likely to be the aqueous solvent or the hydroxyl protons, whilst for P{(CH2)3OH}3 an oxidative addition of H 2 is favoured. The protic nature of 3 and 4 was illustrated by the H-D exchange observed in d2-water. Dihydrides 3 and 4 reacted with carbon monoxide to yield the dicarbonyl cations [Rh(CO)2(P(CH) 2OH)3)3]+ (8) and [Rh(CO) 2(P(C6H5)(CH2OH)2) 3]+ (9). The analogous experiment with [RhH 2(P{(CH2)3OH}3)4] + resulted in phosphine exchange, although our experimental evidence points to the possibility of more than one fluxional process in solution.

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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 cis-Dioxoruthenium(VI) Complex as Active oxidant of Chloride and Organic Substrates; Preparation, Characterization, and Reactivity of cis-2+ (6,6′-Cl2bpy = 6,6′-dichloro-2,2′-bipyriridine)

Oxidation of cis-2+ with CeIV gave cis-2+, isolated as the diamagnetic ClO4- salt, which rapidly oxidizes Cl- (to Cl2) and a wide variety of organic substrates (tetrahydrofuran to butyrolactone and cyclohexane to cyclohexanone)

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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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Clusters metalliques moleculaires synthetises par voie radiolytique

The radiolytic reduction of metal ions in alcohols has been achieved under CO atmosphere.Under such conditions, metal reduction, ligation and aggregation processes compete, leading to metal complexes and molecular clusters.These products are interesting for catalytic purposes.We report here the radiolytic synthesis of compounds of Fe, Ru, Os, Co, Ir, Rh, Pt, Cu, Ag, and of some intermetallic compounds.These syntheses are carried out under very mild temperature and pressure conditions (i.e., room temperature and at most 1 atmosphere of CO).Factors favoring a high nuclearity are the concentration, the high atomic number, a weak ligand/metal ratio.It is shown that chloride ions are inhibitors of complete reduction.

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

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Transient nonlinear optics of organometallic fullerene: Research on iron(III) and ruthenium(III) derivatives of C60

We synthesized and investigated ultrafast third-order optical response of iron(III) (Fe(III)) and ruthenium(III) (Ru(III)) coordinated fullerene derivatives, which were based on our former reported C60(NH2CN)5 series, at 830 nm. The Fe(III), which is electron deficient and blocks the intramolecular charge-transfer process, reduces the optical nonlinearity of the complexes. However, Ru(III), even it is also electron deficient, enhanced the optical nonlinearity for an order of magnitude. By analyzing the infrared spectrum, a possible effect of linked multi-fullerene molecule system is supposed.

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

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Kinetics and mechanistic study of the ruthenium(III) catalyzed oxidative deamination and decarboxylation of L-valine by alkaline permanganate

The kinetics of ruthenium(III) catalyzed oxidation of L-valine by permanganate in alkaline medium at a constant ionic strength has been studied spectrophotometrically. The reaction between permanganate and L-valine in alkaline medium exhibits 2:1 stoichiometry (KMnO4:L-valine). The reaction shows first-order dependence on the concentration of permanganate and ruthenium(III) and less than unit-order dependence on the concentrations of L-valine and alkali. The reaction rate increases both with an increase in ionic strength and a decrease in solvent polarity of the medium. Initial addition of reaction products did not significantly affect the rate. A mechanism involving the formation of a complex between catalyst and substrate has been proposed. The activation parameters were computed with respect to the slowest step of the mechanism.

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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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NEUTRON SCATTERING STUDY OF HYDROGEN ON RUTHENIUM SULFIDE.

Incoherent inelastic neutron scattering (IINS) has been used to characterize hydrogen adsorption sites on ruthenium sulfide at 300 K. Hydrogen resides on sulfur anions to form SH groups, yielding two nondegenerate bending modes at 600 and 710 cm** minus **1. A smaller feature near 370 cm** minus **1 is assigned to a hydrogen-coupled lattice mode. Complementary hydrogen adsorption and H//2-D//2 exchange data further suggest that the active sites for hydrogen adsorption may be coordinatively unsaturated S-S anion pairs which provide sufficient electron density and satisfy the dual-site requirement necessary for hydrogen adsorption.

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