09/16/21 News Some scientific research about (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The kinetics of intermolecular ene-yne metathesis (EYM) with the Hoveyda precatalyst (Ru1) has been studied. For 1-hexene metathesis with 2-benzoyloxy-3-butyne, the experimental rate law was determined to be first-order in 1-hexene (0.3-4 M), first-order in initial catalyst concentration, and zero-order for the terminal alkyne. At low catalyst concentrations (0.1 mM), the rate of precatalyst initiation was observed by UV-vis and the alkyne disappearance was observed by in situ FT-IR. Comparison of the rate of precatalyst initiation and the rate of EYM shows that a low, steady-state concentration of active catalyst is rapidly produced. Application of steady-state conditions to the carbene intermediates provided a rate treatment that fit the experimental rate law. Starting from a ruthenium alkylidene complex, competition between 2-isopropoxystyrene and 1-hexene gave a mixture of 2-isopropoxyarylidene and pentylidene species, which were trappable by the Buchner reaction. By varying the relative concentration of these alkenes, 2-isopropoxystyrene was found to be 80 times more effective than 1-hexene in production of their respective Ru complexes. Buchner-trapping of the initiation of Ru1 with excess 1-hexene after 50% loss of Ru1 gave 99% of the Buchner-trapping product derived from precatalyst Ru1. For the initiation process, this shows that there is an alkene-dependent loss of precatalyst Ru1, but this does not directly produce the active catalyst. A faster initiating precatalyst for alkene metathesis gave similar rates of EYM. Buchner-trapping of ene-yne metathesis failed to deliver any products derived from Buchner insertion, consistent with rapid decomposition of carbene intermediates under ene-yne conditions. An internal alkyne, 1,4-diacetoxy-2-butyne, was found to obey a different rate law. Finally, the second-order rate constant for ene-yne metathesis was compared to that previously determined by the Grubbs second-generation carbene complex: Ru1 was found to promote ene-yne metathesis 62 times faster at the same initial precatalyst concentration.

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

09/16/21 News Awesome Chemistry Experiments For Ruthenium(III) chloride

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A series of functionalized analogues of 1,4,7-trithiacyclononane has been synthesized and the effects of functionalization on their co-ordination chemistry investigated.The substituents were introduced via substituted 1,2-dibromopropanes, by cyclization with 3-thiapentane-1,5-dithiolate in the form of its molybdenum complex (2-).The functionalized macrocycles were then displaced from the metal by additional 3-thiapentane-1,5-dithiolate.A series of complexes (n+) (M = Ag, Hg, Cu, Ni, Co or Fe; L = 2-methyl-1,4,7-trithiacyclononane, the simplest of the new ligands) was prepared.Spectroscopic and electrochemical studies revealed that any effects of substitution on the ring conformational preferences were not manifested in the stability or electrochemistry of the complexes.Molecular-mechanics calculations suggest that no alterations in conformational preferences are caused by a single substitution.Attempts to synthesize analogues with two vicinal methyl groups yielded only polymeric products.

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

09/16/21 News Top Picks: new discover of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The synthesis of small organic molecules as probes for discovering new therapeutic agents has been an important aspect of chemical-biology. Herein we report a reagent-based, diversity-oriented synthetic (DOS) strategy to probe chemical and biological space via a “Click, Click, Cyclize” protocol. In this DOS approach, three sulfonamide linchpins underwent cyclization protocols with a variety of reagents to yield a collection of structurally diverse S-heterocycles. In silico analysis is utilized to evaluate the diversity of the compound collection against chemical space (PC analysis), shape space (PMI) and polar surface area (PSA) calculations.

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

09/16/21 News Top Picks: new discover of Tetrapropylammonium perruthenate

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N,N,N?,N?-Tetramethylethylenediamine dioxide (TMEDAO2) was explored as a more atom economical co-oxidant for the Ley-Griffith oxidation of alcohols to aldehydes. TMEDAO2 was found to selectivity oxidise benzylic and allylic alcohols in comparable yields to that of the standard Ley-Griffith co-oxidant (NMO). Importantly TMEDAO2 facilitated tandem Ley-Griffith-Wittig reactions with stabilised ylides, in good to excellent yields, without the requirement of anhydrous conditions.

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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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Sep-21 News Properties and Exciting Facts About Ruthenium(III) chloride

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New compounds have the formula: STR1 wherein R, R1, X and Y have the meanings described herein. Methods are set forth for synthesizing these compounds and using these compounds to treat diseases associated with amyloidosis, such as Alzheimer’s disease, maturity onset diabetes mellitus, familial amyloid polyneuropathy, scrapie, and Kreuzfeld-Jacob disease.

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

Sep-21 News Properties and Exciting Facts About Tetrapropylammonium perruthenate

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There are disclosed compounds of formula (I) STR1 and pharmaceutically acceptable salts thereof which are useful as antagonists of GnRH and as such may be useful for the treatment of a variety of sex-hormone related conditions in both men and women.

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

Sep-21 News Can You Really Do Chemisty Experiments About (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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Studies towards the total synthesis of the natural product radicicol are described that employ a late-stage esterification and aromatization by trapping a ketene intermediate. The subsequent biomimetic aromatization of the resultant triketo ester gave highly functionalized resorcylates. Two distinct methods were examined that trap the ketene intermediate through either an intermolecular or intramolecular process. In the first approach, the synthesis of the resorcylate was followed by a ring-closing metathesis, which gave the macrolactone and protected precursors to monocillin I. In the second approach, an intramolecular ketene trapping was examined as an alternative to close the macrocycle and form the resorcylate macrolactone. These studies showcased a wide range of sensitive functional groups that tolerated the aromatization reaction conditions, which started from the corresponding dioxinone precursors. Copyright

Sometimes chemists are able to propose two or more mechanisms that are consistent with the available data.Quality Control of: (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride, If a proposed mechanism predicts the wrong experimental rate law, however, the mechanism must be incorrect.Welcome to check out more blogs about 301224-40-8, in my other articles.

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

15-Sep-21 News Discovery of Dichloro(benzene)ruthenium(II) dimer

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The dinuclear RuII arene complexes [{(eta6-arene) RuCl}2(mu-2,3-dpp)](PF6)2, arene = indan (1), benzene (2), p-cymene (3), or hexamethylbenzene (4) and 2,3-dpp = 2,3-bis(2-pyridyl)pyrazine, have been synthesized and characterized. Upon irradiation with UVA light, complexes 1 and 2 readily underwent arene loss, while complexes 3 and 4 did not. The photochemistry of 1 was studied in detail. In the X-ray structure of [{(eta6-indan)RuCl}2(mu-2,3- dpp)](PF6)2 (1), 2,3-dpp bridges two RuII centers 6.8529(6) A apart. In water, aquation of 1 in the dark occurs with replacement of chloride with biexponential kinetics and decay constants of 100 ± 1 min-1 and 580 ± 11 min-1. This aquation was suppressed by 0.1 M NaCl. UV or visible irradiation of 1 in aqueous or methanolic solution led to arene loss. The fluorescence of the unbound arene is ?40 times greater than when it is complexed. Irradiation of 1 also had a significant effect on its interactions with DNA. The DNA binding of 1 is increased after irradiation. The non-irradiated form of 1 preferentially formed DNA adducts that only weakly blocked RNA polymerase, while irradiation of 1 transformed the adducts into stronger blocks for RNA polymerase. The efficiency of irradiated 1 to form DNA interstrand cross-links was slightly greater than that of cisplatin in both 10 mM NaClO4 and 0.1 M NaCl. In contrast, the interstrand cross-linking efficiency of non-irradiated 1 in 10 mM NaClO 4 was relatively low. An intermediate amount of cross-linking was observed when the sample of DNA already modified by non-irradiated 1 was irradiated. DNA unwinding measurements supported the conclusion that both mono- and bifunctional adducts with DNA can form. These results show that photoactivation of dinuclear RuII arene complexes can simultaneously produce a highly reactive ruthenium species that can bind to DNA and a fluorescent marker (the free arene). Importantly, the mechanism of photoreactivity is also independent of oxygen. These complexes, therefore, have the potential to combine both photoinduced cell death and fluorescence imaging of the location and efficiency of the photoactivation process.

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

15-Sep-21 News Archives for Chemistry Experiments of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Ring-opening metathesis (ROM) of various unsaturated, constrained bicyclic ring systems has been investigated with the use of commercial ruthenium-based catalysts. Starting from various cyclodienes, the corresponding derived bicyclic lactone, lactam, and isoxazoline derivatives were submitted to ROM under ethenolysis. These functionalized, strained bicyclic systems afforded novel highly-functionalized diolefinated heterocyclic scaffolds in ROM reactions with stereocontrol, through the conservation of the configuration of the stereogenic centers of the starting compounds.

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