Extracurricular laboratory:new discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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This paper presents a density functional theory study of the ruthenium-catalyzed olefin metathesis reactions. The ligand binding energy has been calculated in the first generation of Grubbs-type (PCy3)2-Cl2Ru=CHPh (pre)catalyst, as well as in the heteroleptic (pre)catalytic systems in which a N-heterocyclic carbene, NHC, ligand substitutes a single phosphine. In agreement with experiments PCy3 coordinates more strongly to Ru in the heteroleptic (pre)catalysts than in the Grubbs-type (pre)catalyst. Moreover, ethene coordination and insertion into the Ru-alkylidene bond in the above-mentioned systems, as well as in the Hofmann type catalytic system with a cis-coordinated phosphane ligand, has been studied. The calculated insertion barrier for the NHC systems are lower than that of the (PCy3)2Cl2Ru=CHPh system. This is consistent with the higher activity experimentally observed for the NHC-based system.

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

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

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Novel eight-membered ring unsaturated lactams were synthesized and tested as monomers for the ruthenium-catalyzed ring-opening metathesis polymerization (ROMP). The reaction of a N-protected cyclic alkeneamine was also investigated. The Grubbs’ benzylidene complexes RuCl2(=CHPh)(PCy3)2 or RuCl2(=CHPh)(PCy3)(IMesH2) and selected ruthenium-arene species bearing either phosphine or stable Arduengo-type N-heterocyclic carbene ligands served as catalyst precursors. In most cases, isomerization of the starting materials took place and only 1-benzyl-l-aza-2-ketocyclooct-5-ene afforded a polymeric product. This polyamide was characterized by numerous analytical techniques.

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

Simple exploration of Tetrapropylammonium perruthenate

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Compounds having Formula 1 wherein the symbols have the meaning defined in the specification are inhibitors of the cytochrome P450RAI (retinoic acid inducible) enzyme, and are used for treating diseases responsive to treatment by retinoids.

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

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

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A series of alkenyl phenylboronic acid pinacol esters has been synthesized via an olefin cross-metathesis reaction of vinylphenylboronic acid pinacol ester derivatives. After catalytic hydrogenation, the resulting boronates were coupled via a microwave-mediated Suzuki-Miyaura reaction to afford a library of biarylethyl aryl and biarylethyl cycloalkyl derivatives. A complementary reaction sequence involved an initial Suzuki-Miyaura coupling.

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

Can You Really Do Chemisty Experiments About Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 32993-05-8, Application In Synthesis of Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

The migration of a phenyl group from phosphorus to the coordinated ruthenium center in complexes (eta6-arene)[eta2-Ph 2PC(R)=C(R?)O]RuCl, 2 [arene = 1,3,5-Me3C6H3 or C6Me6; R = H or Me; R? = But], occurs in methanol at reflux. The reaction is favored by the addition of KOAc and affords selectively the stable phosphinito enolato derivatives (eta6-arene)[eta2-Ph-(MeO)PC(R)=C(R?)O]RuPh. In contrast, the reaction of complexes 2 with methanol and K2CO3 preserves the functional ligand and affords selectively the hydride derivatives (eta6-arene)[eta2-Ph 2PC(R)=C(R?)O]RuH. The cleavage of the ruthenium-chlorine bond in complexes 2 is also the preliminary step involved in the coupling process of functional phosphino enolato ligands with 1-alkynes HC=CR?. The reaction results in the formation of complexes {(eta6-arene)Ru[eta3-CH=C(R?)C(R)(PPh 2)C(R?)=O]}(PF6) [R = H or Me, R? = But or Ph, R? = H, Me, Ph, p-MeC6H4, or SiMe3], the isomerization of which into complexes {(eta6-arene)Ru-[eta3-CH(PPh 2)C(R?)=C(R)C(R?)=O]}(PF6), [R? = But, R? = H, Me, Ph, or p-MeC6H4] occurs only when R = H. The isomerization consists of an intramolecular [1,3]-migration of a phosphorus-carbon bond and is catalyzed by the fluoride anion. When R? = H, a subsequent cleavage of the ruthenium-carbon bond foreshadows the formation of (eta6-C6Me6)[eta1-Ph 2-PCH2CH=CHC(=O)But]RuCl2, 11. Thus, starting from the precursor (eta6-C6Me6)[eta1-Ph 2-PCH2C(=O)But]RuCl2, the process achieves formally an insertion of ethyne into the starting functionalized phosphorus-carbon bond. The scarcely isolable complexes {(eta6-arene)Ru-[eta3-C(=CH2)C(R)(PPh 2)C(R?)=O]Ru}(PF6) [R = H or Me, R? = But or Ph] reveal an easy cleavage of the functionalized phosphorus-carbon bond. This cleavage is the preliminary step involved in the formation of metallafuran complexes {(eta6-arene)(Ph2PX)Ru[eta2-C(CH 3)=CRC(R?)=O]}(PF6) [X = Cl or F, R = H or Me, R? = But or Ph], which implies also the capture of a halide anion by phosphorus in a transient intermediate.

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

A new application about Ruthenium(III) chloride

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Resonance Raman (RR) and optical spectroelectrochemical titrations of the cis,cis-[(bpy)2Ru-(OH2)]2O4+ ion (denoted [3,3] to indicate the formal oxidation state of the Ru-O-Ru unit) were made over the range 0.8-2.0 V vs Ag/AgCl in 0.5 M trifluoromethanesulfonic acid; the results revealed sequential accumulation of three higher oxidation states. Two of these states were identified by redox titration with Os(bpy)32+ as one-electron ([3,4]) and four-electron oxidized species ([5,5]); spectroscopic analysis of reaction products formed upon mixing the [3,3] and [5,5] ions indicated that the third oxidation state is a two-electron oxidized species ([4,4]). The [5,5] ion underwent first-order decay to the [4,4] ion with a rate constant, k ? 9.5 x 10-3 s-1, that was nearly identical with the catalytic turnover rate for O2 evolution, k(cat) ? 1.3 x 10-2 s-1 measured under comparable conditions. The [4,4] ion underwent degradation more slowly to the [3,4] ion, which was stable on these time scales. An analogue bearing 4,4′- dimethyl-2,2′-bipyridine ligands exhibited very similar behavior, except that the oxidation steps were shifted by ~50 mV to lower potentials. 18O isotope labeling experiments on the underivatized complex established that there was no oxygen exchange at the bridging mu-oxo position during catalytic turnover. Frozen solutions of the [5,5] ion displayed unusual low-temperature spectroscopic features, including the following: (i) a narrow g = 2.02 axial EPR signal exhibiting an apparent six-line hyperfine interaction from a minor component; (ii) a concentration-dependent broad rhombic EPR signal in mixtures also containing the [4,4] ion; and (iii) a concentration-dependent replacement of its characteristic ruthenyl Ru=O stretching mode at 818 cm-1 in the RR spectrum when chemically oxidized with Ce4+ by an 18O isotope sensitive set of three bands in the 650 cm-1 region. The RR spectrum of this new species is consistent with further coordination of the terminal oxo ligands by Ce4+ to form additional ligand bridges.

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

Can You Really Do Chemisty Experiments About (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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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.246047-72-3, Name is (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium, molecular formula is C46H65Cl2N2PRu. In a Article,once mentioned of 246047-72-3, Safety of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

A simple and efficient asymmetric synthesis of novel sp3-rich pyrrolidine chemical scaffolds over five steps starting from simple ketones is described. Key steps involve the use of tert-butanesulfinamide as a chiral auxiliary to perform an asymmetric Tsuji?Trost allylation, with subsequent cross-metathesis with an acrylate ester and reduction of the sulfinimine/cyclisation of the resulting amine giving the pyrrolidine scaffolds in high yields and diastereoselectivites. By removing the chiral auxiliary and functionalising the ester group, the resulting scaffold core can be further derivatised.

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

Brief introduction of Dichloro(benzene)ruthenium(II) dimer

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The invention relates to the field of pharmaceutical chemistry and specifically discloses an aryl ruthenium-beta-carboline complex and its preparation method and application. The aryl ruthenium-beta-carboline complex is [Ru(Eta6-arene)(N-N)Cl](PF6), wherein Eta6-arene is aryl ligand p-cymene(p-cymene, CYM) or benzene(benzene, Ben), N-N is beta-carboline alkaloid derivative1-(2-pyridine)-9H-pyridine[3,4-b]indole(L1), 1-(2-quinoline)-9H-pyridine[3,4-b]indole(L2) or 1-(2-imidazole)-9H-pyridine[3,4-b]indole(L3). The complex provided by the invention has very outstanding activity in in-vitro antitumor screening. In addition, in comparison with cancer cell lines, toxicity of the complex to normal cells is greatly reduced, and the complex has a good potential for development of antitumor drugs.

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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 first example of Ru-catalyzed intramolecular annulation of alkynes with amides via formyl translocation has been developed, which provides an efficient approach for the synthesis of 1H-indole-3-carbaldehydes. The Royal Society of Chemistry 2012.

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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 the three key building blocks (65, 98, and 100) required for the total synthesis of the proposed structure of azaspiracid-1 (1a) are described. Key steps include a TMSOTf-induced ring-closing cascade to form the ABC rings of tetracycle 65, a neodymium-catalyzed internal aminal formation for the construction of intermediate 98, and a Nozaki-Hiyama-Kishi coupling to assemble the required carbon chain of fragment 100. The synthesized fragments, obtained stereoselectively in both their enantiomeric forms, were expected to allow for the construction of all four stereoisomers proposed as possible structures of azaspiracid-1 (1a-d), thus allowing the determination of both the relative and absolute stereochemistry of the natural product.

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