Sep 2021 News Extracurricular laboratory:new discovery of Dichloro(benzene)ruthenium(II) dimer

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The synthesis of the cationic Pd complex [Pd(dmba)(PCH2-oxazoline)]Cl [PCH2-oxazoline = 2-oxazoline-2-ylmethyl)diphenylphosphine] (2) has allowed for the first time the observation of hemilabile behaviour for a phosphinooxazoline ligand. This molecular dynamics is stopped upon removal of the chloride anion, by reaction with either NH4PF6, which retains the cationic nature of the complex, or ButOK. The latter reaction leads to the formation of the first example of a Pd complex bearing an anionic phosphinooxazoline ligand, [Pd(dmba){Ph2PCH – -…C( – -…N)CH2CH2O}], abreviated [Pd(dmba)(PCH-oxazoline)] (7), the anionic charge resulting from the monodeprotonation of the PCH2 group. Following this methodology, the Ru complex [RuCl(p-cymene){Ph2PCH – -…C( – -…N)CH2CH2O}], abreviated [RuCl(eta6-p-cymene)(PCH-oxazoline)] (8) and containing this four-electron chelating anionic ligand, was prepared and shown to be more reactive for the catalytic transfer hydrogenation of acetophenone in propan-2-ol than the analogous complex bearing the neutral phosphinooxazoline ligand PCH2-oxazoline. The crystal structure of cis-[Pd{Ph2PCH – -…C( – -…N)CH2CH2O}2], abbreviated cis-[Pd(PCH-oxazoline)2] (6), was determined by X-ray diffraction.

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

Sep 2021 News Discovery of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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Aromatic stars containing hexa-pyridine, -bipyridine and -terpyridine branches are synthesised with or without the central Fe(eta5-C5H5)+ group and coordinated to ruthenium(II) polypyridine moities to construct hexa- and hepta-nuclear hexa-bipyiridine and -terpyridine complexes.

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

06/9/2021 News New explortion of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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A novel ruthenium(II) complex, [Ru(bpy)2(pipipH2)](ClO4)2 · H2O (1) (pipipH2 = 2-(4-(1H-phenanthro[9,10-d]imidazol-2-yl)phenyl)-1H- imidazo[4,5-f][1,10] phenanthroline, bpy = 2,2?-bipyridine) has been found to act as a luminescent pH switch with extraordinary sensitivity through protonation and deprotonation of the bis-imidazole-containing ligand pipipH2 in aqueous solution at room temperature.

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

06/9/2021 News Can You Really Do Chemisty Experiments About Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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Cerium-based materials such as ceria are increasingly used in catalytic reactions. We report here the synthesis of the first Ce-based metal-organic layer (MOL), Ce6-BTB, comprising Ce6 secondary building units (SBUs) and 1,3,5-benzenetribenzoate (BTB) linkers, and its functionalization for photocatalytic hydrogen evolution reaction (HER). Ce6-BTB was postsynthetically modified with photosensitizing [(MBA)Ir(ppy)2]Cl or [(MBA)Ru(bpy)2]Cl2 (MBA = 2-(5?-methyl-[2,2?-bipyridin]-5-yl)acetate, ppy = 2-phenylpyridine, bpy = 2,2?-bipyridine) to afford Ce6-BTB-Ir or Ce6-BTB-Ru MOLs, respectively. The proximity of photosensitizing ligands and Ce6 SBUs in the MOLs facilitates electron transfer to drive photocatalytic HER under visible light with turnover numbers of 1357 and 484 for Ce6-BTB-Ir and Ce6-BTB-Ru, respectively. Photophysical and electrochemical studies revealed a novel dual photoexcitation pathway whereby the excited photosensitizers in the MOL are reductively quenched and then transfer electrons to Ce6 SBUs to generate CeIII centers, which are further photoexcited to CeIII? species for HER.

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

6-Sep-2021 News Top Picks: new discover 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, COA of Formula: C20H16Cl2N4Ru

A pyridyl triazole (pyta) modified sucrose ligand was prepared in a seven step synthesis using D-glucose as the protection group for D-fructose and starting from commercially available sucrose. After complexation with Ru(bpy)2Cl2 precursor, the sucrose-conjugated Ru complex of the general formula [Ru(bpy)2(L)]Cl2 was formed. Acidic cleavage of the D-glucose unit led to the first D-fructose conjugated metal complex via D-fructose C6 in literature. Additionally, pyta-modified D-fructose via C1 and the corresponding Ru complex were synthesized. All compounds were analyzed by Rf values, specific rotation, NMR, IR, UV/Vis and fluorescence spectroscopy, mass spectrometry and elemental analysis.

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

Sep 2021 News Extracurricular laboratory:new discovery of Dichloro(benzene)ruthenium(II) dimer

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Condensation of (R)-2-aminobutanol with salicylaldehyde and 2-pyrrolecarbaldehyde gave the chiral chelate ligands HLL1* and HLL2*, respectively. The diastereomeric complexes (RRu,RC)- and (SRu,RC)-[(eta6-arene)Ru(LL 1*)Cl], eta6-arene = p-cymene (1a/1b), eta6-arene = benzene (2a/2b)1 and (RRu,RC)- and (SRu,RC)[(eta6-arene)Ru(LL 2*)Cl], eta6-arena = p-cymene (3a/3b), eta6-arene = benzene (4a/4b), which only differ in the ruthenium configuration, were prepared by the reaction of [(eta6-arene)RuCl2]2 with the anion of the corresponding ligand HLL*. X-ray analyses of 1a/1b and 3a/ 3b showed a structural peculiarity. The unit cell of these complexes contained diastereomers with the same configuration at the carbon atoms but opposite configuration at the metal centers in a 1:1 ratio. Weak intramolecular O-H…Cl hydrogen bridges were formed in all the complexes. 1H-NMR studies demonstrated the configurational lability at the Ru center. The iodo complexes (RRu,RC)- and (SRu,RC)-[(eta6-p-cymene)Ru(LL*)I], LL* = LL1* (5a/5b) and LL* = LL2* (6a/6b), were synthesized by halogen exchange.

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

Sep 2021 News Properties and Exciting Facts About Dichloro(benzene)ruthenium(II) dimer

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Chemistry is an experimental science, and the best way to enjoy it and learn about it is performing experiments.Introducing a new discovery about 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, COA of Formula: C12H12Cl4Ru2.

The invention belongs to the field of anti-tumor research, discloses a double-nuclear […] complex preparation method and its in the topoisomerase inhibiting and application in treating tumor. […] complexes of the present invention the cationic part of the structure shown in formula I of. The invention optimizes the binuclear […] complex preparation process, the raw material cost is low, the reaction time is short. The resulting complex has high purity, has good water-solubility and excellent spectral properties. The invention binuclear […] complex has very high DNA is inserted into the combining ability, thus having extremely high topoisomerase inhibitory activity, and better anti-tumor effect, one of the complex-induced human prostate cancer cell 22 Rv1 late apoptosis of capacity than cisplatin, is a very application the value of potential anti-tumor medicament. (by machine translation)

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

03/9/2021 News Archives for Chemistry Experiments of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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Ru(bpy)32+ (bpy = 2,2′-bipyridyl) has been covalently attached to n-type SnO2 via condensation of surface hydroxyl groups with ruthenium (4-(trichlorosilylethyl)-4′-methyl-2,2′-bipyridine)bis(2,2′-bipyridine) bis(hexafluorophosphate)).A thick coating (ca. 1000 layers, based on the surface hydroxyl group concentration) was produced, presumably via oligomerization of hydrolyzed -SiCl3 groups.The coating, which was stable to organic solvents as well as to aqueous acids and bases, gave reversible cyclic voltammograms, with peak potentials shifted slightly from those of aqueous Ru(bpy)32+, but the number of electroactive molecules corresponding only to a few layers.The coated electrode gave a photocurrent about twice that observed for SnO2 in contact with aqueous 4mM Ru(bpy)32+, with a slightly red-shifted excitation spectrum.Only a small fraction of the electroactive molecules appeared to participate in excited-state electron transfer, although a steady-state current was supported, presumably by slow electron transfer from the outer layers.Prolonged illumination produces extensive hydrolysis of the outer layers of the coating, but a modest reduction of electroactivity, and only a slight decrease in photocurrent.The photocurrent increases with applied potential, then reaches a plateau, and falls off again near the reduction potential of Ru(bpy)32+*; the falloff is attributed to back-electron transfer via tunnelling through the thin space charge layer.

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

03/9/2021 News Extended knowledge of Dichloro(benzene)ruthenium(II) dimer

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We developed a Ru/hemilabile-ligand-catalyzed nucleophilic aromatic substitution (SNAr) of aryl fluorides as the limiting reagents. Significant ligand enhancement was demonstrated by the engagement of both electron-rich and neutral arenes in the SNAr amination without using excess arenes. Preliminary mechanistic studies revealed that the nucleophilic substitution proceeds on a eta6-complex of the Ru catalyst and the substrate, and the hemilabile ligand facilitates dissociation of products from the metal center.

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

3-Sep-2021 News Top Picks: new discover of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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Three new [Ru(bpy)2X]+ complex ions, where bpy represents bipyridyl ligand and X denotes pyridyl diazolate or pyrazinyl diazolate coordination site, have been computationally designed and synthesized as pH-sensitive molecules. The choice of pyridyl and pyrazinyl moieties allows for the nitrogen content to vary, whereas the influence of the protonation site is quantified by using 1,2-diazolate and 1,3-diazolate derivatives. The absorption and emission properties of the deprotonated and protonated complex ions were characterized by UV-vis and photoluminescence spectroscopy as well as by time-dependent density functional theory. Protonation causes (1) a strong blue shift in the lowest energy 3MLCT ? S0 emission wavelengths, (2) a substantial increase in the emission intensity, and (3) a change in the character of the corresponding 3MLCT emitting states. The blue shift in the emission wavelength becomes less pronounced when the nitrogen content in the X-ligand increases and when going from 1,2- to 1,3-diazolate derivatives. The contrast in the emission intensity of the protonated/deprotonated forms is the highest for the complex ion, containing a 2-pyridyl derivative of the 1,2-diazolate. The complex ions are suggested as potential pH-responsive materials based on change in the color and intensity of the emitted radiation. The broad impact of the research demonstrates that the modification of the nitrogen content and position within the protonable ligands is an effective approach for modulation of the pH-optosensing properties of Ru-polypyridyl complexes.

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