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Design and application of a reflux modification for the synthesis of organometallic compounds using microwave dielectric loss heating effects

A commercially available microwave oven has been modified so that synthese involving the refluxing of organic solvents can be safely and conveniently undertaken.The application of this technique for accelerating the rates of reactions leading to the synthesis of some commonly used organometallic and coordination compounds are described.

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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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Targeting nucleus DNA with a cyclometalated dipyridophenazineruthenium(II) complex

Recently, coordinatively saturated and substitutionally inert Ru(II) complexes have been investigated as anticancer agents. Herein a cyclometalated Ru(II) complex, [Ru(bpy)(phpy)(dppz)]+, was found to be rapidly taken up by cancer cells, and nearly 90% of the complex accumulated in the nuclei of cancer cells after a 2 h incubation. The anticancer activity of this complex was screened against a panel of cancer cell lines. Remarkably, it exhibited IC50 values that were an order of magnitude lower than those of cisplatin. This complex also displayed potencies superior to those of cisplatin against 3D tumor spheroids. Further studies revealed that the high DNA binding affinity of [Ru(bpy)(phpy)(dppz)]+ resulted in effective disruption of the binding of transcription factor NF-kappaB to DNA sequences, thereby inhibiting cellular transcription and leading to irreversible cancer cell apoptosis. Our work provides new insights into understanding the biological interactions and anticancer molecular mechanisms of DNA-specific Ru(II) polypyridyl complexes.

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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, DNA Cleavage Activity, Cytotoxicity, Acetylcholinesterase Inhibition, and Acute Murine Toxicity of Redox-Active Ruthenium(II) Polypyridyl Complexes

Four mononuclear [(L-L)2Ru(tatpp)]2+ and two dinuclear [(L-L)2Ru(tatpp)Ru(L-L)2]4+ ruthenium(II) polypyridyl complexes (RPCs) containing the 9,11,20,22-tetraazatetrapyrido[3,2-a:2?,3?-c:3??,2??-l:2???,3???-n]pentacene (tatpp) ligand were synthesized, in which L-L is a chelating diamine ligand such as 2,2?-bipyridine (bpy), 1,10-phenanthroline (phen), 3,4,7,8-tetramethyl-1,10-phenanthroline (Me4phen) or 4,7-diphenyl-1,10-phenanthroline (Ph2phen). These Ru?tatpp analogues all undergo reduction reactions with modest reducing agents, such as glutathione (GSH), at pH 7. These, plus several structurally related but non-redox-active RPCs, were screened for DNA cleavage activity, cytotoxicity, acetylcholinesterase (AChE) inhibition, and acute mouse toxicity, and their activities were examined with respect to redox activity and lipophilicity. All of the redox-active RPCs show single-strand DNA cleavage in the presence of GSH, whereas none of the non-redox-active RPCs do. Low-micromolar cytotoxicity (IC50) against malignant H358, CCL228, and MCF7 cultured cell lines was mainly restricted to the redox-active RPCs; however, they were substantially less toxic toward nonmalignant MCF10 cells. The IC50 values for AChE inhibition in cell-free assays and the acute toxicity of RPCs in mice revealed that whereas most RPCs show potent inhibitory action against AChE (IC50 values <15 mum), Ru?tatpp complexes as a class are surprisingly well tolerated in animals relative to other RPCs. Note that a catalyst decreases the activation energy for both the forward and the reverse reactions and hence accelerates both the forward and the reverse reactions.Application In Synthesis of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), you can also check out more blogs about15746-57-3

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

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Photochemical, photophysical and redox properties of novel fulgimide derivatives with attached 2,2?-bipyridine (bpy) and [M(bpy) 3]2+ (M = Ru and Os) moieties

Fulgimides monosubstituted with [M(bpy)3]2+ (M = Ru, Os; bpy = 2,2?-bipyridine) chromophore units and with a single bpy group were synthesized and investigated as components of conceivable dinuclear photochromic switches of luminescence. The E-, Z- and closed-ring (C) photoisomer forms of the bpy-bound fulgimide were successfully separated by semi-preparative HPLC. The same procedure failed, however, in the case of the [M(bpy)3]2+-substituted fulgimides. Energy transfer from the excited photochromic unit to the metal-bpy centre competes with the fulgimide cyclization, reducing the photocyclization quantum yields by approximately one order of magnitude compared to the non-complexed fulgimide-bpy ligand (phiEC = 0.17, phiEZ = 0.071, phiZE = 0.15 at lambdaexc = 334 nm). The cycloreversion of the fulgimide-bpy ligand is less efficient (phiCE = 0.047 at lambdaexc = 520 nm). The intensity of the 3MLCT-based luminescence of the metal-bpy chromophore (in MeCN, phideaer = 6.6 ¡Á 10-2 and taudeaer = 1.09 mus for Ru; phideaer = 6.7 ¡Á 10-3 and taudeaer = 62 ns for Os) is not affected by the fulgimide photoconversion. These results and supporting spectro-electrochemical data reveal that the lowest triplet excited states of the photochromic fulgimide moiety in all its E-, Z- and closed-ring forms lie above the lowest 3MLCT levels of the attached ruthenium and osmium chromophores. The actual components are therefore unlikely to form a triad acting as functional switch of energy transfer from [Ru(bpy)3]2+ to [Os(bpy)3]2+ through the photochromic fulgimide bridge. The Royal Society of Chemistry 2009.

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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 of new phenanthroline-based heteroditopic ligands – Highly efficient and selective fluorescence sensors for copper(II) ions

The heteroditopic phenanthroline derivatives 5,6-bis(2-pyridylcarboxamido)- 1,10-phenanthroline (H2L1) and 5,6-bis[(4-methoxy-2- pyridyl)carboxamido]-1,10-phenanthroline (H2L2) have been prepared and characterized, together with their luminescent ruthenium(II) complexes [Ru(bpy)2(H2L1,2)]-(PF 6)2 and [Ru(H2L1) 3](PF6)2 and the corresponding iron(II) complex [Fe(H2L1)3](PF6)2. In these complexes, the metal ion is coordinated by the bidentate phen site of H2L. The luminescence of the ruthenium complexes (lambda ex = 450 nm, lambdaemca. 620 nm) is completely quenched by Cu2+ ions in the micromolar concentration range and, to a lesser extent, by other metal ions. At pH 5, the response of the luminescent sensors is highly Cu2+-selective. Heterodinuclear complexes [Ru(bpy) 2(LM)](PF6)2, [Ru(LM)3](PF 6)2, and [Fe(LM)3](PF6)2 have been isolated for M = Cu2+, Ni2+, Co2+, and Pd2+. It is suggested that M is coordinated to the tetradentate N4 site of L by two deprotonated amide N atoms and two pyridyl groups. This coordination type is confirmed by the EPR spectrum of the compound [Ru II(bpy)2(L1CuII)](PF 6)2. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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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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Structure and properties of diastereoisomers of a ruthenium(II) complex having a pyridylpyrazoline derivative as a ligand

Diastereoisomers of a heteroleptic ruthenium complex, [Ru(bpy)2L]2+ (bpy = 2, 2?-bipyridine, L = 5-(4-nitrophenyl)-1-phenyl-3-(2-pyridyl)-2-pyrazoline) have been isolated. Two isomers have quite similar redox potentials and show MLCT absorptions in the region of 400 to 500 nm with similar absorption maxima at room temperature. By contrast, quite different emission maxima and lifetimes are observed at 77 K.

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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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Photolabile Compounds

The present invention describes Photolabile Compounds methods for use of the compounds. The Photolabile Compounds have a photoreleasable ligand, which can be biologically active, and which is photoreleased from the compound upon exposure to light. In one embodiment, the light is visible light, which is not detrimental to the viability of biological samples, such as cells and tissues, in which the released organic molecule is bioactive and can have a therapeutic effect.

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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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Discovery and investigation of anticancer ruthenium-arene Schiff-base complexes via water-promoted combinatorial three-component assembly

The structural diversity of metal scaffolds makes them a viable alternative to traditional organic scaffolds for drug design. Combinatorial chemistry and multicomponent reactions, coupled with high-throughput screening, are useful techniques in drug discovery, but they are rarely used in metal-based drug design. We report the optimization and validation of a new combinatorial, metal-based, three-component assembly reaction for the synthesis of a library of 442 Ru-arene Schiff-base (RAS) complexes. These RAS complexes were synthesized in a one-pot, on-a-plate format using commercially available starting materials under aqueous conditions. The library was screened for their anticancer activity, and several cytotoxic lead compounds were identified. In particular, [(eta6-1,3,5-triisopropylbenzene)RuCl(4-methoxy-N-(2- quinolinylmethylene)aniline)]Cl (4) displayed low micromolar IC50 values in ovarian cancers (A2780, A2780cisR), breast cancer (MCF7), and colorectal cancer (HCT116, SW480). The absence of p53 activation or changes in IC50 value between p53+/+ and p53-/- cells suggests that 4 and possibly the other lead compounds may act independently of the p53 tumor suppressor gene frequently mutated in cancer.

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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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Photoinduced electron transfer kinetics of linked Ru-Co photocatalyst dyads

Two new supramolecular photocatalyst dyads based on the [Ru(2,2?-bipyridine)3]2+ photosensitizer linked to a macrocyclic Co(II)tetra(pyridyl) catalyst for proton reduction are reported. The dyads differ primarily in the bridging ligand which links the molecular modules; the first being a short and flexible linker, and the second a longer and electronically conjugated linker. Ultrafast transient optical spectroscopy was used to monitor the photoinduced kinetics of the dyads following visible excitation of the photosensitizer module. Direct comparison of transient spectra and kinetics indicates that there are indeed substantial differences between the ultrafast transient optical spectroscopy of the dyads, but there is no indication of oxidative quenching of the photosensitizer module by the catalyst module. These initial design and characterization studies of the linked Ru(II)?Co(II) dyads provide an important foundation for advanced designs of systems for efficient solar energy conversion by molecular architectures.

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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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Relative stability of half-sandwich eta6-benzene Ru(II) complexes of tridentate (2-pyridyl)alkylamine ligands of varying chelate ring-size: Nucleophilic addition of hydride ion onto the benzene ring

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