Some scientific research about (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The synthesis of a series of ruthenium-based metathesis catalysts featuring imine donors chelated through the alkylidene group is described. The relative placement of the imine carbon-nitrogen double bond (exocyclic vs endocyclic) has a major impact on the initiation behavior. When used in metathesis applications, catalysts with an endocyclic imine bond show latent behavior and a high degree of tunability. The incorporation of additional donor atoms is an additional strategy for controlling initiation behavior. These latent catalysts could be useful in high-temperature applications.

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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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Vacancies: Protonation of the ruthenium carbide compounds [Cl 2(L)(PR3)Ru?C:] gives the 14-electron four-coordinate ruthenium phosphonium alkylidenes [Cl2(L)Ru= CH(PR3)]+[B(X)4]- (see scheme). These compounds which already have a vacant coordination site provide direct access to the active species in olefin metathesis catalysis and thus very fast initiation.

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

Top Picks: new discover of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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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, Computed Properties of C31H38Cl2N2ORu

Certain dienynes give cyclorearrangement by tandem cyclopropanation/ring-closing alkene metathesis, triggered by either a ruthenium carbene or noncarbene ruthenium(II) precatalyst. The process represents a variation of enyne metathesis where presumed cyclopropyl carbene intermediates undergo a consecutive ring-closing metathesis. A mechanistic proposal is offered, and sequential use of catalysts provided a tandem ring-closing enyne/alkene metathesis product. 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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For the first time, a deconjugative electrophilic fluorodesilylation reaction was accomplished. gamma-Silyl butenamides were treated with Selectfluor to provide alpha-fluoro-beta,gamma-unsaturated amides. Other sources of electrophilic fluorine were not efficient or gave protodesilylated side products. The electrophilic fluorodesilylation reaction was followed by a ruthenium-catalyzed cross-metathesis of the resulting functionalized allylic fluoride. The fluorodesilylation/cross-metathesis sequence is ideal for the synthesis of fluoro analogues of symbioramide.

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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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The decomposition of a series of ruthenium metathesis catalysts has been examined using methylidene species as model complexes. All of the phosphine-containing methylidene complexes decomposed to generate methylphosphonium salts, and their decomposition routes followed first-order kinetics. The formation of these salts in high conversion, coupled with the observed kinetic behavior for this reaction, suggests that the major decomposition pathway involves nucleophilic attack of a dissociated phosphine on the methylidene carbon. This mechanism also is consistent with decomposition observed in the presence of ethylene as a model olefin substrate. The decomposition of phosphine-free catalyst (H2lMes)(Cl) 2Ru=CH(2-C6H4-O-i-Pr) (H2lMes = 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene) with ethylene was found to generate unidentified ruthenium hydride species. The novel ruthenium complex (H 2lMes)-(pyridine)3(Cl)2Ru, which was generated during the synthetic attempts to prepare the highly unstable pyridine-based methylidene complex (H2lMes)(pyridine)2(Cl) 2Ru=CH2, is also reported.

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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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The total syntheses of the Lythracea alkaloids (+)-vertine and (+)-lythrine are described. Enantioenriched pelletierine is used as a chiral building block and engaged into a two step pelletierine condensation leading to two quinolizidin-2-one diastereomers in a 8:1 ratio. The major product is used in the synthesis of (+)-vertine via aryl-aryl coupling and ring closing metathesis to provide a Z-alkene alpha to the lactone carbonyl function. The same procedure was used for (+)-lythrine after base induced epimerization of the main quinolizidin-2-one diastereomer. Alternative classical ring closure strategies like macrolactonisation or aryl-aryl coupling failed.

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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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The effects of isopropyl substituents and molar concentration of diastereomeric esters toward the formation of nine-membered unsaturated lactones, in the context of the synthesis of the intermediates of the antihypertensive drug aliskiren, have been studied

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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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Understanding the stability and reactivity of the propagating species is critical in living polymerization. Therefore, most living olefin metathesis polymerizations require the stabilization of the catalyst by coordination of external ligands containing Lewis basic heteroatoms, e.g., phosphines and pyridines. However, in some cases, chemists postulated that the propagating metal carbene could also be stabilized by olefin chelation. Here, we disclose that stable 16-electron olefin-chelated Ru carbenes play a key role in previously reported living/controlled ring-opening metathesis polymerization of endo-tricyclo[4.2.2.02,5]deca-3,9-diene and cyclopolymerization of 1,8-nonadiynes using Grubbs catalysts. We successfully isolated these propagating species during polymerization and confirmed their olefin-chelated structures using X-ray crystallography and NMR analysis. DFT calculations and van ‘t Hoff plots from the equilibrium between olefin-chelated Ru carbenes and 3-chloropyridine (Py)-coordinated carbenes revealed that entropically favored olefin chelation overwhelmed enthalpically more stable Py-coordinated Ru carbenes at room temperature. Therefore, olefin chelation stabilized the propagating species and slowed down the propagation relative to initiation, thereby lowering polydispersity. This finding provides a deeper understanding of the olefin metathesis polymerization mechanism using Grubbs catalysts and offers clues for designing new controlled/living polymerizations.

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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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Syntheses of carbohydrate-functionalized platinum complexes resembling presently employed cytostatics were performed. Mono-allylated sugar substrates obtained in two steps from glucose and galactose were connected with 2-allyl diethyl malonate by cross-metathesis. Following hydrogenation and acidic cleavage of the ester and alkylidene functionalities gave dicarboxylated glycoconjugates, which were transformed into their diammine platinum complexes. The antitumor activities of these platinum complexes were checked by sensitivity testing with 11 lung cancer cell lines. The novel glucose-platinum complex proved to be comparable to the drug carboplatin.

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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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The applicability of ruthenium alkylidenes as initiators in the ring opening metathesis polymerization (ROMP) of cyano group containing liquid crystalline norbornene derivatives has been investigated. Complexes featuring N-heterocyclic carbenes as the co-ligands like RuCl2(H2IMes)(PCy3)(=CHPh) polymerized (±)-exo,endo-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid bis-[5-(4?-cyano-biphenyl-4-yloxy)pentyl] ester, while RuCl2(PCy3)2(=CHPh) failed. Especially RuCl2(H2IMes)(=CH-o-(Pr2i)O-C 6H4) proved to be an effective initiator, operating also in ambient conditions. The corresponding side chain liquid crystalline polymers were isolated in high yields and showed considerably narrow polydispersities. The thermal properties of the polymers were compared to the corresponding polymers prepared by a molybdenum based initiator system. Only subtle differences were found, proving at the first time the suitability of ruthenium initiators for the preparation of cyano group substituted side chain liquid crystalline polymers.

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