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Epoxidation of cyclohexene catalyzed by transition-metal substituted alpha-titanium arsenate using tert-butyl hydroperoxide as an oxidant

Epoxidation of cyclohexene, using transition-metal substituted alpha-titanium arsenate {alpha-TiMA, where M = Cu(II), Co(II), Mn(II), Fe(III), Cr(III), and Ru(III)} as a catalyst and dry tert-butyl hydroperoxide as an oxidant, was studied. In the epoxidation reaction, cyclohexene was oxidized to cyclohexene oxide, cyclohexenol, and cyclohexenone. A maximum selectivity for epoxidation of cyclohexene (89.89%) was observed for alpha-TiRuAs/dryTBHP system after 4 hr of reaction when concentrations of catalyst and substrate were 0.20 and 20 mmole, respectively. A mechanism was proposed, which satisfactorily explained the catalytic activity of the alpha-TiMAs/dry/TBHP system for the epoxidation of cyclohexene.

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

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Core-shell structured microcapsular-like Ru@SiO2 reactor for efficient generation of COx-free hydrogen through ammonia decomposition

The core-shell structured microcapsular-like Ru@SiO2 reactor is proved to be the most efficient material known to date for COx-free hydrogen production via ammonia decomposition for fuel cells application. The very active Ru core particles can retain good stability even at high temperatures (up to 650C) thanks to the protection of the inert SiO 2 nano-shell.

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

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Catalytic alkenylation of phenylpyridines with terminal alkynes by a [12]metallacrown-6 ruthenium(II) compound

Two new [12]metallacrown-6 compounds, [M6II(SMe) 12] [M = Ru (1), Zn (2)], were constructed from a dimethyl sulfoxide decomposed methylthiol product to doubly bridged metal centers. The Ru II compound can prompt alkenylation reactions of phenylpyridlnes with alkynes to generate monoalkenylated arylpyrldines in moderate yields with high regioselectivity and stereoselectivity.

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

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Dendrimers with a photoactive and redox-active [Ru(bpy)3]2+-type core: Photophysical properties, electrochemical behavior, and excited-state electron-transfer reactions

We report the synthesis of six new dendrimers built around a [Ru(bpy)3]2+-type core (bpy = 2,2?-bipyridine) and bearing up to 24 4?-tert-butylphenyloxy or 48 benzyl units in the periphery. The metallodendrimers were obtained by complexation of ruthenium trichloride or Ru(bpy)2Cl2 with bipyridine ligands carrying dendritic wedges in the 4,4?-positions. The absorption spectra and luminescence properties (spectra and lifetimes at 77 and 298 K; quantum yields at 298 K) of the six novel compounds are reported. All of them show the characteristic luminescence of the [Ru(bpy)3]2+-type core unit. The dendritic branches protect the luminescent excited state of the core by dioxygen quenching. For the three compounds containing the 4?-tert-butylphenyloxy peripheral units, the electrochemical behavior and the excited-state quenching via electron transfer were also studied. The electrochemical experiments have evidenced an oxidation and three reduction one-electron processes centered in the [Ru(bpy)3]2+-type core and two multielectron oxidation processes involving the dioxybenzene-and oxybenzene-type units of the dendritic branches. The core of the largest dendrimer shows an electrochemical behavior typical of encapsulated electroactive units. The reaction of the luminescent excited state of the [Ru-(bpy)3]2+-type core with three electron-transfer quenchers (namely, methyl viologen dication, tetrathiafulvalene, and anthraquinone-2,6-disulfonate anion) was found to take place by a dynamic mechanism in all cases. The quenching rate constants, obtained by Stern-Volmer kinetic analysis, are compared with those found for the simple [Ru(bpy)3]2+ complex. The results show that, for each quencher, the value of the rate constant decreases with increasing number and size of the dendritic branches. For the second-generation dendrimer containing 24 4?-tert-butylphenyloxy units at the periphery, the rate constant of the reaction with methyl viologen is more than 1 order of magnitude smaller than that of the “naked” [Ru(bpy)3]2+ complex. All the experiments were performed in acetonitrile solution, except for luminescence experiments at 77 K where butyronitrile was used.

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

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Efficient green procedures for the preparation of novel tetraalkynyl-substituted phthalocyanines

This work provides a successful, easy and efficient process for the preparation of metal-free 2(3),9(10),16(17),23(24)-octamethoxyphthalocyanine, [(OMe)8PcH2] (2), and its metal complexes [(OMe)8PcM] (3-11) (M = Zn, Cu, Ni, Mg, Co, Fe, Ru, TiCl and RhCl) by using green energy techniques such as exposure to UV-irradiation as well as microwave irradiation. Two different routes have been used, which involve modifications to that reported in the literature. The results suggest that these techniques drastically reduce the reaction time of metallophthalocyanine [(OMe)8PcM] (3-11) formation from 5-96 h to 5-11 min. The prepared octamethoxyphthalocyanines [(OMe)8PcM] (2-4) (M = H2, Zn, Cu) are used as key materials to synthesize the corresponding novel tetraalkynyl-substituted phthalocyanines 15-17.

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

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Liquid-phase oxidation of alcohols by oxygen and nitrous oxide catalysed by Ru-Co oxide

Chemoselective catalysts in bulk or supported on gamma-Al 2O3 binary oxides RuIV-CoIII (Ru/Co = 1:1-1:2), prepared by co-precipitation, were used for liquid-phase oxidation of saturated and unsaturated primary and secondary alcohols to aldehydes and ketones with O2 or N2O. The catalysts can be separated by filtration and reused. No leaching of Ru or Co in solution was observed. The oxidation is enhanced by the presence of hydration water in the Ru-Co catalyst, which indicates the participation of active RuIV hydroxo species in the reaction. From XRD and TGA, the Ru-Co oxide can be approximated as a hydrous binary oxide comprising the amorphous RuO2 and heterogenite-3R cobaltic acid CoO(OH). The alcohol oxidation appears to occur by a nonradical mechanism, which may be viewed as an oxidative dehydrogenation of alcohols to form an aldehyde or ketone. H2-TPR shows that CoIII practically does not affect the oxidising ability of RuO2. This suggests that the cobalt is likely to enhance catalyst reoxidation by O 2 rather than to play a significant role in the alcohol dehydrogenation. The alcohol oxidation by N2O exhibits a close similarity to the oxidation by O2 but is much less efficient. Much more active catalysts are required to make the oxidation with N2O synthetically useful.

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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, molecular, crystal and electronic structure of [RuCl 3(NO)(PPh3)(HPz)]

The reaction of [RuCl3(NO)(PPh3)2] complex with pyrazole has been examined. The new ruthenium complex – [RuCl 3(NO)(PPh3)(C3 H4N2)] has been obtained and characterised by IR and UV-Vis measurements. Crystal, molecular and electronic structures of the complexes have been determined. The electronic spectrum of the complex was calculated by the TDDFT method.

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

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Substituted pyridazines as ligands in homoleptic (fac and mer) and heteroleptic Ru(ii) complexes

This article reports the preparation of a range of phenyl, pyridyl and pyrazinyl substituted pyridazines via the inverse electron demand [2 + 4] Diels-Alder reaction between 3,6-di(2-pyridyl)-1,2,4,5-tetrazines (bptz) and 3,6-di(2-pyrazinyl)-1,2,4,5-tetrazines (bpztz) and suitable dienophiles including acenaphthalene. The resulting polyaromatic compounds vary systematically in the number of aromatic substituents and the number and position of N-heteroatoms. For four of these compounds, the effect of the molecular changes on the solid-state structures were investigated using single crystal X-ray crystallography. The pyridazines were used as bidentate ligands in {M(ii)(bipy)2} and tris(homoleptic) complexes (M = Fe, Ru). The optical and electrochemical properties of these complexes reflect the electron accepting character of the new ligands. The facial and meridional isomers of the tris complexes could be separated by column chromatography (on silica), thus allowing a spectral comparison of their absorption and emission properties. The solid-state structures of several of the metal complexes are discussed, including that of the facial isomer of the tris Ru(ii) complex of 3,6-bis(2-pyridyl)-4,5-bis(4-pyridyl)pyridazine – a potential preformed geometric motif for the predirected construction of supramolecular assemblies. The Royal Society of Chemistry 2011.

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

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Bi- and tri-nuclear ruthenium(II) complexes containing tetrapyridophenazine as a rigid bridging ligand

The rigid, aromatic bis-tridentate bridging ligand tetrapyrido[2,3-a:3?,2?-c:2?,3?-h:3?,2?-j] phenazine (tpp) allowed the preparation of linear, stable bi- and tri-nuclear complexes of ruthenium(n) exhibiting low energy Ru ? tpp MLCT absorptions and a strong electronic coupling in the mixed-valence state.

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

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A trimetallic mixed Ru(II)/Fe(II) terpyridyl complex with a long-lived excited state in solution at room temperature

The photophysical behavior of a series of mono- and trimetallic Ru(II) and mixed Ru(II)/Fe(II) bis-terpyridyl complexes was examined. The complexes have bridging terpyridyl ligands linked by phenylene-vinylene substituents on the terpyridyl. For the complexes bridged by a single phenylene-vinylene, the lowest-energy excited state is metal-to-ligand charge transfer (MLCT), and excited-state decay is on the 1-10 ns time scale. The complexes with two phenylene-vinylene groups have thermally equilibrated excited states that are localized on the phenylene-vinylene bridge and have much longer lifetimes (>200 ns). Remarkably, the trimetallic complex having an Fe(II) terpyridyl center also has a long-lived excited state, despite the fact that low-energy iron-localized excited states exist on the complex. Copyright

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