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Immobilization of the 2nd generation Hoveyda-Grubbs catalyst HG-II onto well-ordered 2D hexagonal (SBA15) and 3D fibrous (KCC-1) mesostructured silica, which contained tetra-coordinated Al, has been investigated through the Surface Organometallic Chemistry (SOMC) methodology. The main interest of this study lies in the peculiarity of the silica supports, which display a well-defined tetrahedral aluminum hydride site displaying a strong Lewis acid character, [(Si-O-Si)(Si-O-)2Al-H]. The resulting supported Hoveyda-Grubbs catalysts have been fully characterized by advanced solid state characterization techniques (FT-IR, 1H and 13C solid state NMR, DNP-SENS, EF-TEM…). Together with DFT calculations, the immobilization of HG-II does not occur through the formation of a covalent bond between the complex and the Al-modified mesoporous silica as expected, but through an Al?Cl-[Ru]-coordination. It is not surprising that in functionalized olefin metathesis of diethyldiallyl malonate, DEDAM (liquid phase), leaching of the catalyst is observed which is not the case in non-functionalized olefin metathesis of propene (gas phase). Besides, the results obtained in propene metathesis with HG-II immobilized either on SBA15 (dpore = 6 nm) or KCC-1 (dpore = 4 or 8 nm) highlight the importance of the accessibility of the catalytic site. Therefore, we demonstrate that KCC-1 is a promising and suitable 3D mesoporous support to overcome the diffusion of reactants into the porous network of heterogeneous catalysts.

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

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This study aimed at evaluating the impact of the structure of several new olefin metathesis homogeneous catalysts on the performances of a membrane reactor running in a discontinuous mode and equipped with a nanofiltration membrane that was stable in toluene. A set of tailor-made ruthenium-based precatalysts were prepared with a first objective of enhancing the retention of the precatalyst, that is the stable source of the active catalyst, by organic solvent nanofiltration using a commercial polyimide membrane (Starmem 122). These prototype precatalysts were designed taking into account both the molecular weight and the physicochemical characteristics allowing up to 99.6 % retention of the precatalyst in toluene. The new precatalysts were then engaged in a model ring-closing metathesis reaction in the membrane reactor. Results, expressed as the precatalyst apparent turnover number, showed significant differences according to the selected precatalyst, underlining that the membrane reactor advantages and limitations were closely linked to the intrinsic activity of the catalyst. In addition to the retention of the precatalyst by the membrane, a major parameter was the percentage of the precatalyst really activated during the first load of the substrate since that controls the residual amount of precatalyst to be engaged in the following reaction cycle. The main consequence was the proposal of different running modes consisting of a cascade of synthesis in batch mode and separation by the membrane or a membrane reactor process. Copyright

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

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A novel six-coordinated high-valence cationic ruthenium carbyne complex bearing two liable pyridine ligands was prepared in high yield by the reaction of the ruthenium-based complex (IMesH2)(Cl)2(C 5H5N)2RuCHPh [IMesH2=1,3-dimesityl- 4,5-dihydroimida-zol-2-ylidene] with excess iodine as an oxidant in CH 2Cl2 at 25 C under N2. The new ruthenium carbyne-based complex shows moderate to good catalytic activity for ring-closing metathesis reactions. Importantly, no double bond isomerization by-product was produced at elevated reaction temperatures (100 C-137 C) in the reaction catalyzed by the synthesized ruthenium carbyne complex. A mechanism involving the in situ conversion of the ruthenium carbyne through the addition of an iodide to the carbyne carbon was also proposed, and DFT calculations were performed to explain the initiating mechanism.

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

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Cross-metathesis of a wide range of previously unreactive, sterically demanding alkenes can be achieved in fair to excellent yield using a commercially available catalyst by a facile strategy involving reversal of steric preference.

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

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Three ruthenium complexes bearing backbone-monosubstituted CAACs were prepared and displayed dramatic improvement in catalytic efficiency not only in RCM reaction but also in the ethenolysis of methyl oleate, compared to those bearing backbone-disubstituted CAACs.

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

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1,4-Benzoquinones have been found to prevent olefin isomerization of a number of allylic ethers and long-chain aliphatic alkenes during ruthenium-catalyzed olefin metathesis reactions. Electron-deficient benzoquinones are the most effective additives for the prevention of olefin migration. This mild, inexpensive, and effective method to block olefin isomerization increases the synthetic utility of olefin metathesis via improvement of overall product yield and purity. Copyright

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

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301224-40-8, Name is (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, molecular formula is C31H38Cl2N2ORu, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 301224-40-8, Recommanded Product: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

Addition of L = carbon monoxide or aryl isocyanides to the Grubbs second-generation carbene complexes Ru(H2IMes)(CHR)(PCy 3)Cl2 (H2IMes ) 1,3-dimesityl-4,5- dihydroimidazol-2-ylidene; R ) Ph, Me, H, CH=CMe2) triggers carbene insertion into an aromatic ring of the N-heterocyclic carbene supporting ligand, forming Ru{1-mesityl-3-(-7?-R-2?,4?,6?- trimethylcycloheptatrienyl)-4,5-dihydroimidazol-2-ylidene}-L 2(PCy3)Cl2. Insertions are also promoted for other PR3 substituted complexes by carbon monoxide and aryl isocyanides, and for the phosphine-free Hoveyda-Blechert complex Ru(H 2IMes)(CH(i-PrOC6H4))Cl2 by aryl isocyanides and small phosphites but only after initial displacement of the coordinated ether. Heteroatom substituted carbenes do not undergo CO-promoted insertion unless poorer electron donor phosphine (PPh3) and carbene (CH(OC6H4-p-NO2) ligands are both present. Insertion depends on the added ligand, the carbene substituent, and to a lesser degree on the PR3 ligand trans to the N-heterocyclic carbene.

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Reference:
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. 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, Quality Control of: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

The stereoselective syntheses of synargentolide B and its three stereoisomers have been accomplished from L-(+)- and D-(-)-diethyl tartrates, D-ribose, and D-mannitol as chiral pool starting materials. The key step was a tandem ring-closing/cross-metathesis reaction in which lactone formation and fragment coupling were accomplished in one pot. The spectroscopic data of synthetic product 2c were in agreement with those reported for the natural product. Synargentolide B isolated by Rivett et al. and the compound isolated by Pereda-Miranda et al. are not diastereomers, but rather they are identical. Copyright

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

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Microwave-assisted tandem cross metathesis intramolecular Aza-Michael reaction: An easy entry to cyclic beta-amino carbonyl derivatives

Hoveyda-Grubbs catalyst in combination with BF3¡¤OEt2 efficiently promotes tandem cross metathesis intramolecular aza-Michael reaction between enones and unsaturated carbamates resulting in the creation of beta-amino carbonyl units. The use of microwave irradiation dramatically accelerates the process, enhancing the synthetic utility of this methodology for the preparation of these types of derivatives. When enantiomerically enriched ?-branched amines were used as starting materials, the process was also very efficient, although with modest selectivity in the newly created stereocenter. The use of microwave irradiation led to an interesting effect, inverting the selectivity in the addition process. 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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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 Patent£¬once mentioned of 301224-40-8, category: ruthenium-catalysts

METATHESIS CATALYSTS

This invention relates generally to olefin metathesis catalysts, to the preparation of such compounds, compositions comprising such compounds, methods of using such compounds, and the use of such compounds in the metathesis of olefins and in the synthesis of related olefin metathesis catalysts. The invention has utility in the fields of catalysis, organic synthesis, polymer chemistry, and in industrial applications such as oil and gas, fine chemicals and pharmaceuticals.

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