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Ruthenium(II)?arene complexes of diimines: Effect of diimine intercalation and hydrophobicity on DNA and protein binding and cytotoxicity

A series of half-sandwich Ru(II)?arene complexes [Ru(eta6-benzene)(diimine)Cl](PF6) (1?4), where diimine is 1,10-phenanthroline (1), 5,6-dimethyl-1,10-phenanthroline (2), dipyrido[3,2-a:2?,3?-c]phenazine (3) or 11,12-dimethyldipyrido[3,2-a:2?,3?-c]phenazine (4), have been isolated and characterized using analytical and spectral methods. Complex 2 possesses a familiar pseudo-octahedral ?piano-stool? structure. The intrinsic DNA binding affinity of the complexes depends upon the diimine ligand: 3 (dppz) > 4 (11,12-dmdppz) > 2 (5,6-dmp) > 1 (phen). The pi-stacking interaction of extended planar ring of coordinated dppz (3) in between the DNA base pairs is more intimate than that of phen (1), and the incorporation of methyl groups on the dppz ring (4) discourages the stacking interaction leading to a lower DNA binding affinity for 4 than 3. Docking studies show that all the complexes bind in the major groove of DNA. Interestingly, 3 shows an ability to convert supercoiled DNA into nicked circular DNA even at 20 muM concentration beyond which complete oxidative DNA degradation is observed. The protein binding affinity of the complexes decreases in the order 4 > 3 > 2 > 1, and the higher protein binding affinity of 4 illustrates the strong involvement of methyl groups on dppz ring in hydrophobic interaction with protein. Also, 4 cleaves protein more efficiently than the other complexes in the presence of H2O2. It is notable that 2, 3 and 4 display cytotoxicity against human cervical cancer cell lines (SiHa) with potency higher than the currently used drug cisplatin. Acridine orange/ethidium bromide staining studies reveal that 3 induces apoptosis in cancer cells much more efficiently than 4.

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

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Structural characterization and biological evaluation of a clioquinol-ruthenium complex with copper-independent antileukaemic activity

In this study, we present the synthesis, biological characterization, and first crystal structure of an organometallic-clioquinol complex. Combining ruthenium with the established apoptotic agent and 8-hydroxyquinoline derivative, clioquinol, resulted in a complex that induces caspase-dependent cell death in leukaemia cells. This activity is copper independent and is improved compared to the parent compound, clioquinol. The study of the mode of action reveals that this clioquinol-ruthenium complex does not intercalate between DNA base pairs. Additionally, this clioquinol-ruthenium complex shows proteasome-independent inhibition of the NFkappaB signalling pathway, with no effects on cell-cycle distribution. These data suggest a mechanism of action that involves a target profile that is different from that for clioquinol alone. the Partner Organisations 2014.

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

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Tunneling barrier effects on photoinduced charge transfer through covalent rigid rod-like bridges

Four homologous dyads with a phenothiazine donor, rigid variable-length p-xylene bridges, and a ruthenium(ll) tris(2,2′-bipyridine) acceptor were synthesized. Photoexcitation of these donor-bridge-acceptor molecules in the presence of excess methylviologen generates a highly oxidizing Ru(lll) intermediate, which triggers an intramolecular phenothiazine-to-ruthenium(lll) electron transfer that is mediated by the oligo-p-xylene spacers. The rates for this process were determined using transient absorption spectroscopy, and they are found to decrease exponentially with increasing donor-acceptor distance. This decrease occurs with an attenuation factor beta of 0.77 A-1 and is substantially stronger than for analogous donor-bridge-acceptor molecules where the acceptor is a rhenium(l) tricarbonyl diimine complex (beta = 0.52 A-1). This striking finding is interpreted in terms of a larger barrier to hole tunneling in the ruthenium dyads relative to the rhenium systems.

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

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Effect of diphosphine ligands on ruthenium catalyzed asymmetric hydrogenation of ketones

A series of diphosphines including those that are configurationally flexible were examined in the Ru(II) catalyzed enantioselective hydrogenation of 1-acetonaphthone in the presence of a chiral diamine. These ligands were found to exert significant effects on both the activity and enantioselectivity of Ru(II)-diamine catalysts, with the ligand with the smallest bite angle yielding the lowest conversion and the one with largest bite angle yielding the lowest enantioselection.

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

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Synthesis, characterization, anticancer and antimicrobial study of arene ruthenium(II) complexes with 1,2,4-triazole ligands containing an alpha-diimine moiety

The reaction of the ruthenium arene dimers [(eta6-arene)Ru(mu-Cl)Cl]2 (where arene=benzene or p-cymene) with the ligands 4-benzylidene-3,5-di(2?-pyridyl)-4-amino-1,2,4-triazole (L1), 2-methoxybenzylidene-3,5-di(2?-pyridyl)-4-amino-1,2,4-triazole (L2), 4-methylbenzylidene-3,5-di(2?-pyridyl)-4-amino-1,2,4-triazole (L3) and indole-3-carbaldehyde-3,5-di(2?-pyridyl)-4-amino-1,2,4-triazole (L4) in a 1:2 ratio gives the new complexes [(eta6-arene)RuCl(L)]+ [arene=C6H6 (with L=L1(1), L2(3), L4(7), with PF6- as a counter ion, and L4 (6), with Cl- as a counter ion) or p-cymene with L=L1(2), L2(4), L3(5), L4(8) with PF6- as a counter ion]. All complexes were fully characterized using 1H and 13C NMR, elemental analyses, UV/Vis and IR spectroscopy. The single crystal X-ray structures of ligand L2 and complex 1 have been determined. The structure of 1 has the Ru atom coordinated with the arene group and to the N,N?-bidentate ligand and to the Cl atom. The arene group occupies the apex, while the ligand and the Cl atom are at the base of a pseudo-octahedral three-legged piano stool. The cytotoxicity of these mononuclear complexes was established in the human epithelial colorectal adenocarcinoma cell line (Caco-2) and for selectivity in the non-cancerous human embryonic kidney cell line (HEK293), using 5-fluorouracil (5-FU) as the reference anticancer drug. Compounds 1 and 7 were relatively inactive toward the Caco-2 tumor cells (IC50>200), while complexes 2-5 showed moderate anti-proliferative properties (IC50>100-200). Compound 6, however, displayed better anti-proliferative properties with an IC50 value lower than that of the reference drug, 5-FU, and was therefore further investigated for its antimicrobial activity against six Gram-positive and four Gram-negative bacteria.

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

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Thiolato-bridged RuIIAgRuII trinuclear complex composed of bis(bipyridine)ruthenium(II) units with chelating 2-aminoethanethiolate: Conversion to a disulfide-bridged RuIIRu II dinuclear complex

The reaction of [Ru(solvent)2(bpy)2]2+ (bpy = 2,2?-bipyridine) with Haet (2-aminoethanethiol) in ethanol/water in the presence of Ag+ gave a thiolato-bridged RuIIAgRu II trinuclear complex, [Ag{Ru-(aet)(bpy)2} 2]3+, in which two [RuII(aet)(bpy) 2]+ units are linked by an AgI atom. When this complex was treated with HCl in acetonitrile/water, a disulfide-bridged Ru IIRuII dinuclear complex, [Ru2(cysta)(bpy) 4]4+ (cysta = cystamine), was produced as a result of the removal of an AgI atom and the autoxidation of thiolato groups. It was found that the dinuclear structure in [Ru2(cysta)-(bpy) 4]4+ is reverted back to [Ag{Ru(aet)(bpy) 2}2]3+ by treatment with Ag+ assisted by Zn reduction.

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

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Highly stereoselective cyclopropanation of diazo Weinreb amides catalyzed by chiral Ru(II)-: Amm -Pheox complexes

The first highly stereoselective cyclopropanation of diazo Weinreb amides with olefins was accomplished using chiral Ru(ii)-Amm-Pheox complex 7a to give the corresponding chiral cyclopropyl Weinreb amides in high yields (up to 99%) with excellent diastereoselectivities (up to 99:1 dr) and enantioselectivities (up to 96% ee).

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

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The reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at the same temperature.37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2. In a Article£¬once mentioned of 37366-09-9, COA of Formula: C12H12Cl4Ru2

Acceptorless, neat, ruthenium-catalyzed dehydrogenative cyclization of diols to lactones

We report the dehydrogenation of 1,4-butanediol to gamma-butyrolactone catalyzed by soluble ruthenium complexes without solvent or a hydrogen acceptor. An alkylphosphine version of ruthenium bis-phosphine diamine catalysts has been prepared and was found to be the longest-lived catalyst for the conversion of 1,4-butanediol to gamma-butyrolactone. The catalytic production of gamma-butyrolactone from 1,4-butandiol with this catalyst is simple to conduct, environmentally friendly, and highly efficient.

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

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Synthesis, antiproliferative activity and apoptosis-promoting effects of arene ruthenium(II) complexes with N, O chelating ligands

New half sandwich arene ruthenium(II) complexes of the type [Ru(arene)Cl(L)] (where arene = benzene and p-cymene, L = thiophene benzhydrazone ligands) have been synthesized from the reactions of the neutral precursor [Ru(arene) (mu-Cl) Cl]2 and the corresponding benzhydrazone ligand. All the complexes were completely characterized by elemental analysis and additionally by IR, UV?Vis, 1H NMR and ESI-MS spectroscopic methods. The solid state structures of the complexes 6 and 7 were determined by single-crystal X-ray diffraction analysis, which exhibit typical pseudo-octahedral geometry around the metal centre. The antiproliferative activity of the complexes was evaluated on cancerous (HeLa, MDA-MB-231, and Hep G2) and noncancerous (NIH3T3) cell lines. In general, complexes containing electron releasing OCH3 substituent have potential anticancer activity than those incorporating H, Cl and Br substituents. Moreover, the p-cymene complexes show more cytotoxicity than benzene derivatives, suggesting that the substituent at arene plays a vital role in the biological activity of the compounds. Further, an apoptotic mechanism of cell death in MDA-MB-231 was confirmed by AO-EB, Hoechst 33258 staining and annexin-V/PI double-staining techniques. In addition, the extent of DNA fragmentation in cancer cells was studied by comet assay.

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

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Disilametallacycles as a platform for stabilizing M(II) and M(IV) (M = Fe, Ru) centers: Synthesis and characterization of half-sandwich complexes and their application to catalytic double silylation of alkenes and alkynes

A series of group 8 half-sandwich disilametallacycles, (eta6- arene)MII(Me2SiC6H4SiMe 2)L and (eta6-arene)MIV(H) 2(Me2SiC6H4SiMe2) (M = Fe, Ru) in the formal oxidation states of M(II) and M(IV) were synthesized and characterized. Both the M(II) and the M(IV) oxidation states were effectively stabilized by the disilametallacycle skeleton, and facile interconversion between (eta6-arene)MII-dinitrogen, (eta6- arene)MII-carbonyl, and (eta6-arene)M IV-dihydride complexes bearing a disilaferracycle framework was accomplished. These M(II) and M(IV) complexes can easily generate coordinatively unsaturated 16e disilametallacycles, (eta6-arene)M II(Me2SiC6H4SiMe2), by dissociation of L or H2, and stoichiometric and/or catalytic double silylation of alkenes and alkynes was realized thorough this 16e intermediate.

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