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Aryloxybenzylidene ruthenium chelates: Synthesis, structure and catalytic activity in olefin metathesis

New aryloxybenzylidene ruthenium chelates behave like a promising latent catalyst of olefin metathesis. The catalysts are characterised by substantial stability and catalytic inactivity in their dormant forms and a dramatic increase in activity after addition of a solution of HCl in ether. The mechanism of activation involves protonation of the phenoxide and the formation of a highly catalytically active hydroxybenzylidene ruthenium chelate. Ruthenium aryloxybenzylidene complexes have been synthesised and proved to behave like latent catalysts of olefin metathesis. The mechanism of chemical activation by HCl involves the formation of an isolable catalytically active hydroxybenzylidene complex.

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

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Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex

Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared ?Ru-Hoechsts?, each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus.

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

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246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 246047-72-3, Product Details of 246047-72-3

Exploiting and understanding the selectivity of Ru-N-Heterocyclic carbene metathesis catalysts for the ethenolysis of cyclic olefins to alpha,omega-Dienes

A library of 29 homologous Ru-based olefin metathesis catalysts has been tested for ethenolysis of cyclic olefins toward the goal of selectively forming alpha,omega-diene using cis-cyclooctene as a prototypical substrate. Dissymmetry at the N-heterocyclic carbene (NHC) ligand was identified as a key parameter for controlling the selectivity. The best-performing catalyst bearing an N-CF3 group significantly outperformed the benchmark second-generation Grubbs catalyst in the ethenolysis of cis-cyclooctene. Application of this optimal catalyst to the ethenolysis of various norbornenes allows the efficient synthesis of valuable diene intermediates in good yields. The observed ligand effect trends could be rationalized through univariate and multivariate parameter analysis involving steric and electronic descriptors of the NHC ligand in the form of the buried volume and the 77Se NMR chemical shift, in particular the sigmayy component of the shielding tensor of [Se(NHC)] model compounds, respectively. Natural chemical shift analysis of this chemical shielding tensor shows that sigmayy probes the I-Acceptor property of the NHC ligand, the essential electronic parameter that drives the relative rate of degenerate metathesis and selectivity in ethenolysis with catalysts bearing dissymmetric NHC ligands.

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

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15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 15746-57-3, category: ruthenium-catalysts

Effects of excited state – Excited state configurational mixing on emission bandshape variations in ruthenium – Bipyridine complexes

The 77 K emission spectra of 21 [Ru(L)4bpy]m+ complexes for which the Ru/bpy metal-to-ligand-charge-transfer ( 3MLCT) excited-state energies vary from 12 500 to 18 500 cm -1 have vibronic contributions to their bandshapes that implicate excited-state distortions in low frequency (lf, hnulf < 1000 cm-1), largely metal-ligand vibrational modes which most likely result from configurational mixing between the 3MLCT and a higher energy metal centered (3LF) excited state. The amplitudes of the lf vibronic contributions are often comparable to, or sometimes greater than those of medium frequency (mf, hnumf > 1000 cm-1), largely bipyridine (bpy) vibrational modes, and for the [Ru(bpy)3] 2+ and [Ru(NH3)4bpy]2+ complexes they are consistent with previously reported resonance-Raman (rR) parameters. However, far smaller lf vibronic amplitudes in the rR parameters have been reported for [Os(bpy)3]2+, and this leads to a group frequency approach for interpreting the 77 K emission bandshapes of [Ru(L) 4bpy]m+ complexes with the vibronic contributions from mf vibrational modes referenced to the [Os(bpy)3]2+ rR parameters (OB3 model) and the envelope of lf vibronic components represented by a “progression” in an “equivalent” single vibrational mode (lf1 model). The lf1 model is referenced to rR parameters reported for [Ru(NH3)4bpy]2+. The observation of lf vibronic components indicates that the MLCT excited-state potential energy surfaces of Ru-bpy complexes are distorted by LF/MLCT excited-state/excited-state configurational mixing, but the emission spectra only probe the region near the 3MLCT potential energy minimum, and the mixing can lead to larger distortions elsewhere with potential photochemical implications: (a) such distortions may labilize the 3MLCT excited state; and (b) the lf vibrational modes may contribute to a temperature dependent pathway for nonradiative relaxation.

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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 3,4-dimercapto-3-cyclobutene-1,2-dione-chelated ruthenium carbene catalyst for: Z -stereoretentive/stereoselective olefin metathesis

A ruthenium carbene catalyst chelated with a 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand was synthesized and its molecular structure was determined by single-crystal X-ray diffraction. The Ru catalyst had excellent catalytic activity with high yields and good Z/E ratios for the ring opening metathesis polymerization (ROMP) of norbornene (yield: 96%/Z/E: 86 : 14) and 1,5-cyclooctadiene (yield: 86%/Z/E: 91 : 9) and for ring opening cross metathesis (ROCM) reactions of norbornene/5-norbornene-2-exo, 3-exo-dimethanol with styrene (yields: 64%-92%/Z/E: 97 : 3-98 : 2) or 4-fluorostyrene (yield: 46%-94%/Z/E: 98 : 2). The catalyst also had high Z-stereoretentivity (91 : 9-98 : 2) for cross-metathesis (CM) reactions of terminal olefins with (Z)-2-butene-1,4-diol. More importantly, the catalyst had moderate Z-stereoselectivity for homometathesis reactions of terminal olefins giving cis-olefins as the major products (Z/E ratios of 70 : 30-77 : 23). Like other Ru carbene complexes, the catalyst tolerates many different functional groups. The presented data, supported by DFT calculations, show that our catalyst, bearing a chelating 3,4-dioxocyclobut-1-ene-1,2-dithiolate ligand, exhibits higher stability towards air than Hoveyda’s stereoretentive complex systems.

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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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246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 246047-72-3, Computed Properties of C46H65Cl2N2PRu

Qualitative FT-Raman investigation of the ring opening metathesis polymerization of dicyclopentadiene

This study describes the qualitative analysis of the polymerization reaction of DCPD (DiCycloPentaDiene) and its reaction products. The polymerization was carried out using WCl6/Si(allyl)4 (1), first generation Grubbs’ (2) and second generation Grubbs’ (3) catalysts. When system 1 was used as a catalyst, solution concentration determined whether soluble or insoluble polymer was obtained. When Grubbs’ catalysts were employed, insoluble polymer was formed in all cases. The ring opening metathesis polymerization (ROMP)-reaction and the resulting polymers were monitored in situ via FT-Raman-spectroscopy. Using FT-Raman-spectroscopy, the stereospecific nature of the forming polymer can be determined during the polymerization reaction. The obtained spectra illustrate that the linear polymer has a prevailing cis double bond configuration, while the polymer formed using the 1e generation Grubbs catalyst has a predominant trans double bond configuration. The second generation Grubbs catalyst exhibits a poor stereoselectivity. These results are in accordance to literature data where the stereospecific nature of these polymers where determined using NMR-spectroscopy.

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

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Reference of 246047-72-3. Let¡¯s face it, organic chemistry can seem difficult to learn. Especially from a beginner¡¯s point of view. Like 246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium. In a document type is Article, introducing its new discovery.

Catalyst-controlled asymmetric synthesis of fostriecin and 8-epi-fostriecin

Catalytic asymmetric synthesis of the natural antibiotic fostriecin (CI-920) and its analogue 8-epi-fostriecin and evaluation of their biological activity are described. We used four catalytic asymmetric reactions to construct all of the chiral centers of fostriecin and 8-epi-fostriecin; cyanosilylation of a ketone, Yamamoto allylation, direct aldol reaction, and Noyori reduction, two of which were developed by our group. Catalytic enantioselective cyanosilylation of ketone 13 produced the chiral tetrasubstituted carbon at C-8. Both enantiomers of the product cyanohydrin were obtained with high enantioselectivity by switching the center metal of the catalyst from titanium to gadolinium. Yamamoto allylation constructed the C-5 chiral carbon in the alpha,beta-unsaturated lactone moiety. A direct catalytic asymmetric aldol reaction of an alkynyl ketone using LLB catalyst constructed the chirality at C-9 with the introduction of a synthetically versatile alkyne moiety, which was later converted to cis-vinyl iodide, the substrate for the subsequent Stille coupling for the triene synthesis. Noyori reduction produced the secondary alcohol at C-11 from the acetylene ketone 6 with excellent selectivity. Importantly, all the stereocenters were constructed under catalyst control in this synthesis. This strategy should be useful for rapid synthesis of stereoisomers of fostriecin.

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

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Asymmetrische Katalysen. LXXXII. Enantioselektive Hydrierung von 4-Oxoisophoron

Enantioselective hydrogenation of 4-oxoisophorone 1, catalysed by BINAP-RuII complexes, gives the corresponding saturated diketone 2 in 80percent chemical yield and 50percent enantiomeric excess.By repeated crystallisation from petroleum ether/dichloromethane 4/1 the diketone 2 is obtained optically pure in 25percent total yield.The monoalcohol 3 is formed as a byproduct of the hydrogenation.The formation of 3 can be suppressed by using the monomethyl-eol ether 4 as a substrate.Catalytic hydrogenation of 4 in methanol gives exclusively the dimethylketal 5, which upon acidic hydrolysis is transformed into the diketone 2 in 50percent ee.

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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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Reference of 301224-40-8, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu. In a Patent£¬once mentioned of 301224-40-8

MACROCYCLE DERIVATIVES USEFUL AS INHIBITORS OF BETA-SECRETASE (BACE)

The present invention is directed to macrocycle derivatives, pharmaceutical compositions containing them and their use in the treatment of Alzheimer’s disease (AD) and related disorders. The compounds of the invention are inhibitors of beta-secretase, also known as beta-site cleaving enzyme and BACE, BACE1, Asp2 and memapsin2.

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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.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: Dichloro(benzene)ruthenium(II) dimer

Synthesis, structure, and reactivity of RuII complexes with trimethylsilylethinylamidinate ligands

The mononuclear amidinate complexes [(eta6-cymene)-RuCl(1a)] (2) and [(eta6-C6H6)RuCl(1b)] (3), with the trimethylsilyl-ethinylamidinate ligands [Me3SiC?CC(N-c-C 6H11)2]- (1a-) and[Me3SiC?CC(N-i-C3H7)2] – (1b-) were synthesized in high yields by salt metathesis. In addition, the related phosphane complexes[(eta5- C5H5)Ru(PPh3)(1b)] (4a) [(eta5- C5Me5)Ru(PPh3)(1b)] (4b), and [(eta6-C6H6)Ru(PPh3)(1b)](BF 4) (5-BF4) were prepared by ligand exchange reactions. Investigations on the removal of the trimethyl-silyl group using [Bu 4N]F resulted in the isolation of [(eta6-C 6H6)Ru(PPh3){(N-i-C3H 7)2CC?CH}](BF4) (6-BF4) bearing a terminal alkynyl hydrogen atom, while 2 and 3 revealed to yield intricate reaction mixtures. Compounds 1a/b to 6-BF4 were characterized by multinuclear NMR (1H, 13C, 31P) and IR spectroscopy and elemental analyses, including X-ray diffraction analysis of 1b, 2, and 3. Copyright

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