Discovery of (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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The highest initiation rate of any reported ruthenium-based catalyst was found for the new olefin-metathesis catalyst [(H2IMes)(3-Br-py)2(Cl)2Ru=CHPh] (1), which was synthesized in one step from commercially available reagents. Complex 1 is highly efficient for the cross metathesis of acrylonitrile, which is generally a poor substrate for metathesis reactions (e.g., see scheme). Mes = 2,4,6-trimethylphenyl.

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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 Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

Balanced chemical reaction does not necessarily reveal either the individual elementary reactions by which a reaction occurs or its rate law.Computed Properties of C20H16Cl2N4Ru. In my other articles, you can also check out more blogs about 15746-57-3

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Ru(II)-polypyridine complexes of the general formula [Ru(L1/L2)(phen)2]X2 (1a?6a) and [Ru(L1/L2)(bipy)2]X2 (1b?6b) (where X = ClO4, BF4, PF6; phen = 1,10-phenanthroline, bipy = 2,2?-bipyridine) were prepared by the reaction of [Ru(phen)2Cl2]·2H2O and [Ru(bipy)2Cl2]·2H2O with (E)-5-((4-methoxyphenyl)ethynyl)-N-(pyridin-2-ylmethylene)pyridin-2-amine (L1) and (E)-5-((4-nitrophenyl)ethynyl)-N-(pyridin-2-ylmethylene)pyridine-2-amine (L2) in the presence of NaBF4, NaClO4, and NaPF6. The electrochemical properties of all the complexes indicate reversible redox behavior corresponding to Ru(II)?Ru(III) couple and are susceptible to variation of electron-donating/accepting properties of substituent group on L1 and L2. All complexes showed room temperature luminescence corresponding to pi?pi* intra-ligand charge-transfer (ILCT) transition with chelation enhanced fluorescence and is finely tuned by increasing pi-conjugation, size of counter anions, and variation of substituent group with different electronic effects in the complexes. All the complexes worked as an effective catalyst for the oxidation of benzyl alcohol to corresponding benzaldehyde in good yield at room temperature. (Figure presented.).

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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 (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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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. 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, Formula: C46H65Cl2N2PRu

An expeditious click-click cyclize strategy for the assembly of medium-sized heterocyclic rings is described. The sequence involves the reaction of cycloprop-2-ene carboxylic acids with unsaturated amines to furnish amides, which are further subjected to a Cu-catalyzed directed carbomagnesiation and a ring-closing olefin metathesis reaction. This methodology allows for the efficient preparation of lactams with ring sizes up to 10.

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

Extended knowledge of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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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. 15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru. In a Article,once mentioned of 15746-57-3, HPLC of Formula: C20H16Cl2N4Ru

We have synthesized the complex [Ru(bpy)2(bpy(OH) 2)]2+ (bpy =2,2?-bipyridine, bpy(OH)2 = 4,4?-dihydroxy-2,2?-bipyridine). Experimental results coupled with computational studies were utilized to investigate the structural and electronic properties of the complex, with particular attention paid toward the effects of deprotonation on these properties. The most distinguishing feature observed in the X-ray structural data is a shortening of the CO bond lengths in the modified ligand upon deprotonation. Similar results are also observed in the computational studies as the CO bond becomes double bond in character after deprotonating the complex. Electrochemically, the hydroxy-modified bipyridyl ligand plays a significant role in the redox properties of the complex. When protonated, the bpy(OH)2 ligand undergoes irreversible reduction processes; however, when deprotonated, reduction of the substituted ligand is no longer observed, and several new irreversible oxidation processes associated with the modified ligand arise. pH studies indicate [Ru(bpy)2(bpy(OH) 2)]2+ has two distinct deprotonations at pKa1 = 2.7 and pKa2 = 5.8. The protonated [Ru(bpy)2(bpy(OH) 2)]2+ complex has a characteristic UV/Visible absorption spectrum similar to the well-studied complex [Ru(bpy)3]2+ with bands arising from Metal-to-Ligand Charge Transfer (MLCT) transitions. When the complex is deprotonated, the absorption spectrum is altered significantly and becomes heavily solvent dependent. Computational methods indicate that the deprotonated bpy(O-)2 ligand mixes heavily with the metal d orbitals leading to a new absorption manifold. The transitions in the complex have been assigned as mixed Metal-Ligand to Ligand Charge Transfer (MLLCT).

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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 regioselective ring closing ene-yne metathesis provided an efficient access to different substituted 1-benzazepine scaffolds. The reported synthetic approach could also be used as a powerful tool for the selective formation of a highly functionalizable 2-benzazepine core. This synthetic protocol was even proved to be an efficient way to obtain a functionalizable benzazocine derivative. By modifying the structure of the starting materials, the optimized cyclization finally proved to be a suitable technique to obtain five- and six-membered lactams, enhancing the synthetic application of our method. Five- and six-membered lactams were efficiently prepared by ring-closing metathesis involving the loss of ethylene moiety and affording highly functionalizable compounds showing both electron-withdrawing substituents and electron-donor groups.

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

The Absolute Best Science Experiment for (1,3-Bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(tricyclohexylphosphine)ruthenium

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Pyridine as a stabilizing donor ligand drastically improves the performance of ruthenium monothiolate catalysts for olefin metathesis in comparison with previous versions based on a stabilizing benzylidene ether ligand. The new pyridine-stabilized ruthenium alkylidenes undergo fast initiation and reach appreciable yields combined with moderate to high Z selectivity in self-metathesis of terminal olefins after only a few minutes at room temperature. Moreover, they can be used with a variety of substrates, including acids, and promote self-metathesis of omega-alkenoic acids. The pyridine-stabilized ruthenium monothiolate catalysts are also efficient at the high substrate dilutions of macrocylic ring-closing metathesis and resist temperatures above 100 C during catalysis.

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

Final Thoughts on Chemistry for Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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A series of mixed ligand Ru(II) complexes of 5,6-dimethyl-1,10-phenanthroline (5,6-dmp) as primary ligand and 1,10-phenanthroline (phen), 2,2?-bipyridine (bpy), pyridine (py) and NH3 as co-ligands have been prepared and characterized by X-ray crystallography, elemental analysis and 1H NMR and electronic absorption spectroscopy. The X-ray crystal structure of the complex [Ru(phen)2(bpy)]Cl2 reveals a distorted octahedral coordination geometry for the RuN6 coordination sphere. The DNA binding constants obtained from the absorption spectral titrations decrease in the order, tris(5,6-dmp)Ru(II) > bis(5,6-dmp)Ru(II) > mono(5,6-dmp)Ru(II), which is consistent with the trend in apparent emission enhancement of the complexes on binding to DNA. These observations reveal that the DNA binding affinity of the complexes depend upon the number of 5,6-dmp ligands and hence the hydrophobic interaction of 5,6-dimethyl groups on the DNA surface, which is critical in determining the DNA binding affinity and the solvent accessibility of the exciplex. Among the bis(5,6-dmp)Ru(II) complexes, those with monodentate py (4) or NH3 (5) co-ligands show DNA binding affinities slightly higher than the bpy and phen analogues. This reveals that they interact with DNA through the co-ligands while both the 5,6-dmp ligands interact with the exterior of the DNA surface. All these observations are supported by thermal denaturation and viscosity measurements. Two DNA binding modes – surface/electrostatic and strong hydrophobic/partial intercalative DNA interaction – are suggested for the mixed ligand complexes on the basis of time-resolved emission measurements. Interestingly, the 5,6-dmp ligands promote aggregation of the complexes on the DNA helix as a helical nanotemplate, as evidenced by induced CD signals in the UV region. The ionic strength variation experiments and competitive DNA binding studies on bis(5,6-dmp)Ru(II) complexes reveal that EthBr and the partially intercalated and kinetically inert [Ru(phen)2(dppz)]2+ (dppz = dipyrido[3,2-a:2?,3?-c]phenazine) complexes revert the CD signals induced by exciton coupling of the DNA-bound complexes with the free complexes in solution.

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

The important role of 32993-05-8

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Thermolysis of [CpRuCl(PPh3)2] and NaS 2CNPr2 or NaS2CNMeBu in methanol affords the ruthenium(II) dithiocarbamate complexes, [CpRu(PPh3)(S 2CNPr2)] and [CpRu(PPh3)(S2CNMeBu)], which have been crystallographically characterized. A similar treatment of two equivalents of [CpRuCl(PPh3)2] with the bis(dithiocarbamate) ligand derived from 1,3-homopiperazine affords [{CpRu(PPh3)}2(mu-S2CNC5H 10NCS2)].

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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 Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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The absorption spectra, emission spectra (from 90 to 350 K), luminescence lifetimes (from 90 to 350 K), luminescence quantum yields, luminescence quenching by dioxygen, photochemical behavior, and redox potentials of a caged (4) and a hemicaged (3) Ru(II)-polypyridine complex have been studied and compared with those of the parent compounds Ru(bpy)3(2+) (1) and Ru(5,5′-(EtO2C)2-bpy)3(2+) (2) (bpy = 2,2′-bipyridine).The absorption band in the visible and the emission band of 4 are quite close in energy to the corresponding bands of 1, whereas those of 3 and 2 are red shifted.The oxidation and reduction processes of 3 and 4 take place at more positive potentials than those of 1.A linear correlation between the spectroscopic and electrochemical energies is observed for the four complexes.The luminescence lifetimes of 2 (0.57 mus) and 3 (1.9 mus) are shorter than those of 1 (4.8 mus) and 4 (4.8 mus) in nitrile rigid matrix at 90 K and are much more affected by the melting of the matrix (110-150 K).For T>150 K (i.e., in fluid solution), the luminescence lifetimes of 2 and 3 (0.09 and 0.45 mus) do not change up to 350 K, in contrast with the well-known behavior of 1, where a radiationless activated process with high-frequency factor (A ca. 1E14 s-1) and large activation energy (DeltaE ca. 4000 cm-1) reduces the excited-state lifetime to 0.80 mus at room temperature.The caged complex 4 exhibits a less important radiationless activated process (A ca. 1E10 s-1, DeltaE ca. 2700 cm-1) and maintains a longer lifetime (1.7 mus) at room temperature.In CH2Cl2 solution containing 0.01 M Cl(1-), Ru(bpy)3(PF6)2 undergoes a photodecomposition reaction with Phip = 0.017, whereas the PF6(1-) salts of 2-4 are photoinert (Phip <= 1E-6 for 4).The rate constant for the dioxygen quenching of the luminescent excited state of 4 is ca. 5 times smaller than that of 1.A comparative discussion of the properties of the four complexes is presented.The cage complex 4 exhibits all the properties that make 1 a widely used photosensitizer, with the additional advantages of a longer excited-state lifetime at room temperature in fluid solution and a 1E4 times higher stability toward ligand photodissociation. I hope this article can help some friends in scientific research. I am very proud of our efforts over the past few months and hope to 15746-57-3, help many people in the next few years., Related Products of 15746-57-3

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

Extracurricular laboratory:new discovery of (1,3-Dimesitylimidazolidin-2-ylidene)(2-isopropoxybenzylidene)ruthenium(VI) chloride

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The total synthesis of the natural product RK-397 is based on a new synthetic strategy for assembling polyacetate structures, by efficient cross-coupling of nucleophilic terminal alkyne modules with electrophilic epoxides bearing another alkyne at the opposite terminus. The natural product is constructed from four principal modules: a polyene precursor for carbons 3-9, and three alkyne-terminated modules for carbons 10-16, 17-22, and 23-33. Each module is prepared with control of all stereochemical elements, and the alkynyl alcohols obtained from alkyne-epoxide couplings are converted into 1,3-diols by a sequence of hydroxyl-directed hydrosilylation, C-Si bond oxidation, and stereoselective ketone reduction with induction from the beta-hydroxyl group. The highly convergent nature of our synthetic pathway and the flexibility of the modular synthesis strategy for virtually any stereoisomer can provide access to other members of the polyene-polyol macrolides, including stereoisomers of RK-397.

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