9/29/21 News Craze Concerns Chemists Of Dichloro(benzene)ruthenium(II) dimer

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Ruthenium(II)/dimethyl phenyloxazoline (Ru(II)/dm-Pheox) complex 2a and its macroporous-polymeric-catalyst 4 were found to be very rapid and efficient catalysts in the hydrogen peroxide oxidation of 1,2- and 1,4-dihydroxy arenes. Most of the quinone products were delivered in 99% yield. The polymeric-catalyst 4 could be reused at least five times.

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

09/29/21 News Decrypt The Mystery Of 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

9/29/21 News Machine Learning in Chemistry About Tetrapropylammonium perruthenate

The π-electrons of these planar compounds are free to cycle around the circular arrangements of atoms found in the aromatic moieties. This stems from the resonance found in planar ring systems, like benzene, and 114615-82-6!, Related Products of 114615-82-6

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The Ley?Griffith oxidation, which is catalyzed by tetra-n-propylammonium perruthenate (TPAP, nPr4N[RuO4]), is a popular method for not only controlled oxidation of primary alcohols to aldehydes, but also a host of other synthetically useful transformations. While the fundamental reaction mechanism has recently been elucidated, several key hydrogen-bonding interactions between the reagents were implicated but not investigated. Herein the prevalence of H-bonding between the co-oxidant N-methylmorpholine N-oxide (NMO), the alcohol substrate, water and the perruthenate catalyst is established. These observations help to rationalize the importance of drying the reagents and lead to several practical suggestions.

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

9/29/21 News Exploration Of Everyday Chemical Compounds: Tetrapropylammonium perruthenate

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CCR3 antagonist leads with IC50 values in the muM range were converted into low nM binding compounds that displayed in vitro inhibition of human eosinophil chemotaxis induced by human eotaxin. In particular, 4-benzylpiperidin-1-yl-n-propylureas and erythro-3-(4-benzyl-2-(alpha-hydroxyalkyl)piperidin-1-yl)-n-propylureas (obtained via Beak reaction of N-BOC-4-benzylpiperidine) exhibited single digit nanomolar IC50 values for CCR3.

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

29-Sep News What Unique Challenges Do Researchers Face in Dichloro(benzene)ruthenium(II) dimer

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Over the past 20 years, ruthenium(II)-based dyes have played a pivotal role in turning dye-sensitized solar cells (DSCs) into a mature technology for the third generation of photovoltaics. However, the classic I3-/I- redox couple limits the performance and application of this technique. Simply replacing the iodine-based redox couple by new types like cobalt(3+/2+) complexes was not successful because of the poor compatibility between the ruthenium(II) sensitizer and the cobalt redox species. To address this problem and achieve higher power conversion efficiencies (PCEs), we introduce here six new cyclometalated ruthenium(II)-based dyes developed through ligand engineering. We tested DSCs employing these ruthenium(II) complexes and achieved PCEs of up to 9.4% using cobalt(3+/2+)-based electrolytes, which is the record efficiency to date featuring a ruthenium-based dye. In view of the complicated liquid DSC system, the disagreement found between different characterizations enlightens us about the importance of the sensitizer loading on TiO2, which is a subtle but equally important factor in the electronic properties of the sensitizers.

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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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The ordered structures constructed from an aligner molecule 1o and conjugated polymers (CPs) were efficiently converted into the poly-pseudo-rotaxane structures by the template-assisted ring-closing olefin metathesis (RCM) of olefinic groups at the peripheral positions of 1o. Moreover, the poly-pseudo-rotaxane structures permitted the separation of the crystalline ordered assemblies of CP by size exclusion chromatography and the preservation of the sheet morphologies after the treatment with trifluoroacetic acid. The morphologies and the periodicities of assemblies were also maintained after the retrieving treatments. Copyright

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

9/29/21 News What Kind of Chemistry Facts Are We Going to Learn About Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)

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A couple of challenges comes to mind: improving temperature dependence of relative stabilities of polymorphs would help in identifying enantiotropic relationships. 32993-05-8, Name is Chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II), molecular formula is C41H35ClP2Ru. In a Article,once mentioned of 32993-05-8, Reference of 32993-05-8

Synthesis and structural studies of the ruthenium(II) “sandwich” complexes , , and (R = H, Me) are described.The results of a single crystal X-ray structural study of are discussed. Keywords: Ruthenium; Ruthenocene; Phospharuthenocenes; Fluxionality; Crystal structure

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

29-Sep-21 News Chemical Research in ruthenium-catalysts: Dichloro(benzene)ruthenium(II) dimer

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The abundance and evolving pathogenic behavior of bacterial microorganisms give rise to antibiotic tolerance and resistance which pose a danger to global public health. New therapeutic strategies are needed to keep pace with this growing threat. We propose a novel approach for targeting bacteria by harnessing formate, a cell metabolite found only in particular bacterial species, to activate an antibacterial prodrug and selectively inhibit their growth. This strategy is premised on transfer hydrogenation reaction on a biorthogonal substrate utilizing native formate as the hydride source as a means of uncaging an antibacterial prodrug. Using coordination-directed 3-component assembly to prepare a library of 768 unique Ru?Arene Schiff-base complexes, we identified several candidates that efficiently reduced sulfonyl azide functional group in the presence of formate. This strategy paves the way for a new approach of targeted antibacterial therapy by exploiting unique bacterial metabolites.

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

9/29/21 News 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 invention discloses a metal complex compound ligand, metal complex and its preparation method and application. The invention of the metal complex of the formula IIc are as follows. Metal complex of this invention has the catalytic activity is high, the diversity of the structure and physical properties and the like, for various raw material catalytic application offers a wide range of optimization selection. The invention also discloses various different types of small molecule cyclic catalytic ring-opening polymerization (ROMP) generating various functional polymer new material and its application, structure is as follows: (by machine translation)

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

29-Sep-21 News Search for Chemical Structures By a Sketch: Dichloro(benzene)ruthenium(II) dimer

Learn more about the 37366-09-9., Formula: C12H12Cl4Ru2

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A series of arene Ru(II) salt complexes of the type [(eta6-arene)RuCl(eta2-dppm)]+[ECl3]- (arene = C6H6, p-cymene, 1,3,5-Me3C6H3; E = Ge, Sn) bearing trichlorogermanate and trichlorostannate anions are reported. Starting from the known complexes: [(eta6-C6H6)RuCl2(eta1-dppm)] (1), [(eta6-p-cymene)RuCl2(eta1-dppm)] (3) and the novel complex [(eta6-1,3,5-Me3C6H3)RuCl2(eta1-dppm)] (7) (dppm = 1,1-bis(diphenylphosphino)methane), reactions with SnCl2 or GeCl2(dioxane) respectively afforded, by halide abstraction at the ruthenium(II) centres in 1, 3 or 7 the salts: [(eta6-C6H6)RuCl(eta2-dppm)]+ SnCl3? (2), [(eta6-p-cymene)RuCl(eta2-dppm)]+ SnCl3? (4), [(eta6-C6H6)RuCl(eta2-dppm)]+ GeCl3? (5), [(eta6-p-cymene)RuCl(eta2-dppm)]+ GeCl3? (6), [(eta6-1,3,5-Me3C6H3)RuCl(eta2-dppm)]+ SnCl3? (8) and [(eta6-1,3,5-Me3C6H3)RuCl(eta2-dppm)]+ GeCl3? (9). The trichlorostannate complexes 2, 4 and 8 are extremely rare examples of ruthenium complexes bearing the SnCl3? counter anion, and the complexes 5, 6 and 9 are the first examples of ruthenium trichlorogermanate complexes to be reported. All compounds were isolated in high yields as air stable materials and were spectroscopically characterized by multinuclear NMR: (1H, 31P{1H}, 13C{1H}), Infra-red (IR), UV?Vis, and high resolution electrospray ionization mass spectrometry (HR-ESI-MS), the latter both in (+) and (?) mode. Additionally, single crystal X-ray diffraction analyses of salts 4 and 6 are reported, revealing pseudotetrahedral Ru(II) centres with eta6 bound p-cymene ligands and eta2-bound dppm ligands with statistical disorder on the ECl3- anions (E = Ge (6), Sn (4)). Density functional theory calculations (B3LYP with the basis set 6-31 + G(d,p) for H, C, P and Cl atoms; while for Ru, Ge, and Sn atoms DGDZVP basis set) are reported for salts 4 and 6 revealing localization of the LUMOs on the ruthenium-arene rings and some localization on the chloride atom. Finally, MTT in vitro cytotoxicity assays for the MCF-7 and MDA-MB-231 breast cancer cell lines are reported for all complexes and compared to cisplatin. All complexes show remarkable in vitro cytotoxic activity and most are considerably more cytotoxic than cisplatin in both breast cancer cell lines: IC50 values range from 2.25 muM (compound 2) to 5.97 muM (compound 9) (cisplatin = 5.74 muM) in MCF-7 cells; 2.20 muM (compound 2) to 6.39 muM (compound 5) (cisplatin = 13.98 muM) in MDA-MB-231. Moreover, when compared to non-malignant breast epithelial cells (MCF12A), all complexes exhibit promising selectivity indices (SI) with compound 5 having the highest SI in MCF-7 cells at 4.8; and compound 6 at 3.65 in MDA-MB-231, with most of the other compounds also being considerably more selective than cisplatin on both cell-lines (SI = 2.26 on MCF-7 and 0.93 on MDA-MB-231). A clonogenic assay was conducted for salts 5 and 6 and the results reveal that both compounds inhibited long-term (14 days) survival in both breast cancer cell lines tested indicating these drugs are very promising candidates for pre-clinical studies.

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