29-Sep-21 News Exploration Of Everyday Chemical Compounds: Dichloro(benzene)ruthenium(II) dimer

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The mononuclear complexes [(eta6-arene)Ru(ata)Cl]PF6{ata = 2-acetylthiazole azine; arene = C6H6[(1)PF6]; p-iPrC6H4Me [(2)PF6]; C6Me6[(3)PF6]}, [(eta5-C5Me5)M(ata)]PF6{M = Rh [(4)PF6]; Ir [(5)PF6]} and [(eta5-Cp)Ru(PPh3)2Cl] {eta5-Cp = eta5-C5H5[(6)PF6]; eta5-C5Me5(Cp*) [(7)PF6]; eta5-C9H7(indenyl); [(8)PF6]} have been synthesised from the reaction of 2-acetylthiazole azine (ata) and the corresponding dimers [(eta6-arene)Ru(mu-Cl)Cl]2, [(eta5-C5Me5)M(mu-Cl)Cl]2, and [(eta5-Cp)Ru(PPh3)2Cl], respectively. In addition to these complexes a hydrolysed product (9)PF6, was isolated from complex (4)PF6in the process of crystallization. All these complexes are isolated as hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV-Vis spectroscopy. The molecular structures of [2]PF6and [9]PF6have been established by single-crystal X-ray structure analyses.

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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 Search for Chemical Structures By a Sketch: Dichloro(benzene)ruthenium(II) dimer

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A full account of half-sandwich complexes of ruthenium(II) having three-legged “piano-stool” geometry supported by tridentate (2-pyridyl)alkylamine ligands is presented. Reaction of the dimer [{(eta6-C6H6)RuCl(mu-Cl)}2] with N-methyl-N,N-bis(2-pyridylmethyl)amine (MeL*) in CH3OH in the presence of NH4PF6 affords the complex [(eta6-C6H6)Ru(MeL*)][PF6]2 (1). A similar reaction with N-methyl-N,N-bis(2-pyridylethyl)amine (MeL**), however, affords a non-organometallic Ru(III)-dimeric complex [(MeL* *)2 Ru2III (mu -O) (mu -Cl) Cl2] [PF6] (5) (the composition of this complex has been established by physicochemical method). Nucleophilic addition reaction on 1 with NaBH4 leads to the isolation of a cyclohexadienyl complex [(eta5-C6H7)Ru(MeL*)][PF6] (3). The molecular structure of 1 · 2CH3CN, 3, and previously reported cyclohexadienyl complex [(eta5-C6H7)Ru(MeL)][PF6] (4) [MeL = N-methyl-[(2-pyridyl)ethyl(2-pyridyl)-methyl]amine], obtained from the reaction between NaBH4 and previously reported “piano-stool” complex [(eta6-C6H6)Ru(MeL)][PF6]2 (2), has been confirmed by X-ray crystallography. Solution-state structure of new complexes 1 and 3 has been elucidated by their 1H NMR spectra in CD3CN. The behavior of complex 3 has been investigated with the aid of two-dimensional 1H NMR spectroscopy, as well. An attempt has been made to provide a rationale for the effect of supporting tridentate N-donor ligand [MeL, MeL*, and MeL**], varying in the chelate ring-size on (i) the relative stability of half-sandwich eta6-benzene Ru(II) complexes and (ii) the electrophilicity of Ru(II)-coordinated benzene ring on the nucleophilic addition reactions.

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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

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

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

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

9/28 News Simple exploration of Dichloro(benzene)ruthenium(II) dimer

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Aromatic interactions can greatly affect the stability and interactions of a crystal. They are the strongest such interactions after hydrogen bonding. 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer,molecular formula is C12H12Cl4Ru2, is a conventional compound. this article was the specific content is as follows.37366-09-9

Cyclometalated ruthenium(II) complexes having acridine moieties have been synthesized and characterized by spectroscopic methods. Protonation of the acridine nitrogen of the ruthenium(II) complexes not only causes dynamic equilibrium with remote N-heterocyclic carbene Ru=C complexes but also generates the NAD+/NADH redox function driven by a proton-coupled two-electron transfer accompanying a reversible C-H bond formation in the pyridinium ring.

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

28-Sep-21 News Top Picks: new discover of Dichloro(benzene)ruthenium(II) dimer

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Reaction of the dimers [RuCl2(neta6-arene)] 2 (arene = benzene, p-cymene, mesitylene) with salicyloxazolines in the presence of NaOMe gives complexes [RuCl(R-saloxaz)(arene)] (1-5) which have been fully characterised. Complexes [RuL(iPr-saloxaz)(mes)]Y (L = py, 2-Mepy, 4-Mepy; PPh3; Y- = SbF6 or BPh 4) 6-9 were prepared by treating the chloride 2a with ligand L and NaY (Y- = SbF6 or BPh4) in methanol at reflux. Halide complexes [RuX(iPr-saloxaz)-(mes)] (X = Br, 10; X = I, 11) were synthesised by treating 2a with AgSbF6 then with 1.2 equivalents of KBr or NaI, the methyl complex [RuMe(iPr-saloxaz)(mes)] 12 was synthesised from 2a by reaction with MeLi. Five complexes, [RuCl( iPr-saloxaz)(mes)] 2a, [RuCl(tBu-saloxaz)(p-cymene)] 3b, [RuCl(Ph-saloxaz)(mes)] 5a, [Ru(4-Mepy)(iPr-saloxaz)(mes)][SbF 6] 7, and [Ru(PPh3)(iPr-saloxaz)(mes)][SbF 6] 9, have been characterised by X-ray crystallography. Treatment of complexes 1-5 with AgSbF6 gives cationic species which are enantioselective catalysts for the Diels-Alder reaction of acroleins with cyclopentadiene, the effect of substituents on enantioselectivity has been examined.

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

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

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A cyclopentadienyl ruthenium(II) complex has been immobilized on MCM-41 modified with aminopropyl group through an amide bond formation reaction. FT-IR and UV-vis spectra show successful immobilization of cyclopentadienyl ruthenium complex onto the mesoporous silica surface by utilizing the amino group as a connector. The coordination state of the ruthenium complex is analyzed in detail by XAFS measurements, which indicate that the immobilization process does not influence its coordination geometry. Moreover, the retaining of long range ordering of the mesoporous structure of MCM-41 after grafting is evident from the results of XRD and N2 adsorption-desorption measurements. The resulting material promotes efficiently the hydrosilylation of 1-hexyne to produce vinylsilane with high alpha-selectivity under UV-irradiation at room temperature. Furthermore, the catalyst is recyclable for several catalytic runs without significant loss of its catalytic activity.

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

9/27 News Let’s Talk About Compound: Dichloro(benzene)ruthenium(II) dimer

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The reaction of [RuCl2(eta6-benzene)]2 with aroylthiourea resulted in the formation of Ru(ii) complexes of the type [RuCl2(eta6-benzene)L] (L = monodentate aroylthiourea ligand). The complexes were well characterized using UV-Visible, FT-IR, NMR and mass spectroscopic techniques. Single crystal X-ray diffraction confirmed the monodentate coordination of the ligand through a sulfur atom. The interaction of the Ru(ii) complexes with calf thymus DNA (CT DNA) was investigated using UV-Visible and fluorescence spectroscopic methods, and viscosity measurements. The binding ability of the complexes with bovine serum albumin (BSA) was explored using UV-Visible and fluorescence experiments. The results showed that the complexes interact with the biomolecules with appreciable binding constants. The gel electrophoresis technique was used to demonstrate the unwinding of the supercoiled DNA to its nicked form. The cytotoxicity of the Ru(ii) complexes was screened for a panel of cancer cell lines like HepG2, A549, MCF7 and SKOV3. Complexes 1, 2 and 3 showed modest activity at the concentration of 31.25 mug mL?1 against HepG2 cells. Complexes 1 and 3 displayed moderate cytotoxicity at the concentration of 62.5 mug mL?1 against A549 and SKOV3 respectively. Low cytotoxicity was observed for all the complexes against MCF7. Advantageously, complexes exhibited only less toxicity against Vero normal cells. Further DNA fragmentation, flow cytometry and fluorescence staining [DAPI (blue), FITC (green) and PI (red)] for the detection of apoptosis in HepG2 cells were carried out. The above methods demonstrated that the complexes have a significant ability to induce cell death by apoptosis.

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