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

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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

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 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

28-Sep News A new application about Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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We report two ruthenium(II) polypyridyl complexes with pendant phenol/catechol functionality that act as colorimetric sensors for fluoride ions. Experiments have revealed that hydrogen bond formation occurs with a slight excess of fluoride ion. However, in higher [F-], deprotonation of the O-H functionality resulted. Time-dependent (TD-DFT) calculations at the B3LYP/LANL2DZ level have shown that new bands appear at longer wavelengths upon complexation with fluoride ions. These are of mixed character, MLCT (dpi(Ru) ? pi*(Li/bpy)), and intra- and interligand [pi(L 1) ? pi*(bpy) and pi(L1) ? pi*(L1)] transitions. These complexes also act as sensors for fluoride ions in solvent-water mixtures.

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

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Ru(ii) polypyridyl complexes possessing long wavelength absorption and an efficient DNA photocleavage activity exhibit a potential application in photodynamic therapy (PDT). In this article, we reported a Ru(ii) polypyridyl complex, [Ru(bpy)2(dpb)]2+ (bpy = 2,2?-bipyridine, dpb = 2,3-bis(2-pyridyl)benzoquinoxaline), that exhibits a very long wavelength 1MLCT absorption, with a maximum at 550 nm, and DNA photocleavage activity in anaerobic conditions in the presence of suitable oxidative quenchers, showing a promising potential application in the PDT of hypoxic tumors.

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