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Reduction of 1,2-closo-C2B10H12 followed by treatment with [RuCl2(p-cymene)]2 (p-cymene = C 6H4MeiPr-1,4) affords the 13-vertex ruthenacarborane 4-(p-cymene)-4,1,6-closo-RuC2B10H 12, characterised both spectroscopically and, in two crystalline forms, crystallographically. Although asymmetric in the solid state, having a docosahedral cage architecture with cage C atoms at vertices 1 and 6, this species clearly has Cs symmetry on the NMR timescale at room temperature. However, the fluctional process in operation can be arrested at low temperature, and an activation energy of 43.1 kJ mol-1 is estimated. A computational study of the related species 4-(eta-C6H 6)-4,1,6-closo-RuC2B10H12 reveals that the fluctionality is due to a double diamond-square-diamond process, first suggested by Hawthorne et al for the analogous CpCo species. These calculations yield an activation energy of 40.4 kJ mol-1, in excellent agreement with that derived from experiment. Reduction of 1,2-Ph2-1,2-closo- C2B10H10 followed by treatment with [RuCl 2(eta-C6H6)]2 or [RuCl 2(p-cymene)]2 yields the analogous species 1,6-Ph 2-4-(eta-C6H6)-4,1,6-closo-RuC 2B10H10 and 1,6-Ph2-4-(p-cymene)-4, 1,6-closo-RuC2B10H10, respectively. These C,C-diphenyl compounds were again studied spectroscopically and crystallographically, the p-cymene species again showing two crystalline modifications. In contrast to their CpCo and Cp*Co analogues all three ruthenacarboranes do not undergo isomerisation in refluxing toluene. The Royal Society of Chemistry 2005.

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

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An efficient asymmetric hydrogenation of delta-keto Weinreb amides catalyzed by a Ru-Xyl-SunPhos-Daipen bifunctional catalyst has been achieved. This method afforded a series of enantio-enriched delta-hydroxy Weinreb amides in good yields (up to 93%) and enantioselectivities (up to 99%). This protocol was successfully applied to the synthesis of the key intermediate of (+)-Centrolobine.

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

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2. In a Article,once mentioned of 37366-09-9, Application In Synthesis of Dichloro(benzene)ruthenium(II) dimer

Homo-hetero binuclear cationic complexes with the formulation [(eta 6-arene)RuCl(mu-dpp)(L)]+ (eta6-arene = benzene; L = PdCl2 (1a); PtCl2 (1b), and eta 6-arene = p-cymene; L = PdCl2 (2a); PtCl2 (2b)), [(eta6-arene)RuCl(mu-dpp)(L)]2+(eta 6-arene = p-cymene; L = [(eta6-C6H 6)RuCl] (2c), and [(eta6-C10H 14)RuCl] (2d)) were prepared. Molecular structure of the representative homo binuclear complex [{(eta6-C10H 14)RuCl}(mu-dpp){(eta6-C10H 14)RuCl}](PF6)2 (2d) was determined crystallographically. Weak interaction studies on the complex 2d revealed stabilisation of the crystal packing by weak inter and intra molecular C-H?X (X = F, Cl, pi) and pi-pi interactions. The C-H?F interactions lead to parallel helical chains and encapsulation of counter anion in self-assembled cavity arising from C-H?pi and pi-pi weak interactions.

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

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The synthesis and characterization of binuclear ruthenium complexes [{(eta6-C6H6)Ru}2 (mu-bsh)2] (1), [{(eta6-C10 H14)Ru}2(mu-bsh)2] (2), [{(eta6-C6Me6)Ru}2 (mu-bsh)2] (3), and rhodium complex [{(eta5-C5Me5)RhCl}2 (mu-bsh)] (4) (bsh=N,N?-bis(salicylidine)-hydrazine dianion) are reported. The complexes have been fully characterized by analytical and spectral techniques and unusual coordination mode of the ligand H2bsh has been confirmed by single crystal X-ray analysis of the complex 2. Structural data revealed extensive inter- and intra-molecular C-H?O and C-H?pi interactions and involvement of methyl and isopropyl hydrogen from the p-cymene in hydrogen bonding.

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

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In this article, Ru(ii)-arene-2-pyridinylbenzoxazole complexes [(eta6-p-cymene)RuCl(kappa2-N,N-5-bromo-2-(pyridine-2-yl)benzo[d]oxazole)] (4) and [(eta6-benzene)RuCl(kappa2-N,N-5-bromo-2-(pyridine-2-yl)benzo[d]oxazole)] (5) and Ru(ii)-arene-2-quinolylbenzoxazole complexes [(eta6-p-cymene)RuCl(kappa2-N,N-5-bromo-2-(quinoline-2-yl)benzo[d]oxazole)] (4?) and [(eta6-benzene)RuCl(kappa2-N,N-5-bromo-2-(quinoline-2-yl)benzo[d]oxazole)] (5?) were synthesized and characterized using various spectroscopic techniques. Structural analysis indicates that the Ru(ii) centres are in a distinct mononuclear, one-sided octahedral [RuN6] coordination geometry with two neutral bidentate nitrogen donors in the bromobenzoxazole ligands. All four complexes exhibit three different electronic bands: a sharp band at 300-330 nm due to ligand-to-ligand charge transfer (LLCT); a band around 400 nm due to metal-to-ligand charge transfer; and a small broad peak at around 600 nm due to ligand-to-metal charge transfer. The fluorescence abilities of the four complexes were studied using the LLCT absorption peak as the excitation energy in dimethylsulfoxide: water (1?:?1, v/v), and the quantum yield was found to decrease in the order of 5? > 4? > 4 > 5. Density functional theory calculations reveal that the highest-occupied molecular orbital is primarily located on the benzoxazole ring system, while the lowest-unoccupied molecular orbital is mainly located on the Ru atom, which implies possible charge transfer from ligand to metal. The binding strengths of the Ru(ii) complexes with DNA (5? > 4? > 4 > 5) and bovine serum albumin (4? > 5? > 5 > 4) were on the order of 105-106 and 103-105 M?1, respectively. The conductometric data reveal that all four complexes are non-electrolytic in nature, and viscosity decreases in the order of 5? > 4? > 4 > 5. This might be due to the effective intercalation of 5? compared to the other complexes. DNA and protein docking studies suggest that all the complexes interact with DNA through the minor groove and favourably occupy the active sites of proteins based on dipole-dipole interactions. Gel electrophoresis studies show that all complexes degrade plasmid DNA (1 kb) completely within 1 h of exposure time. MTT assay results indicate that all complexes exhibit highly selective cytotoxicity for two cancer cell lines (Caco-2 and HeLa) with respect to normal HEK-293 cells. Among the complexes, 4? and 5 show the highest cytoselectivities for the Caco-2 and HeLa cell lines, respectively.

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

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Half-Sandwich Iridium and Ruthenium Complexes: Effective Tracking in Cells and Anticancer Studies

Half-sandwich metal-based anticancer complexes suffer from uncertain targets and mechanisms of action. Herein we report the observation of the images of half-sandwich iridium and ruthenium complexes in cells detected by confocal microscopy. The confocal microscopy images showed that the cyclopentadienyl iridium complex 1 mainly accumulated in nuclei in A549 lung cancer cells, whereas the arene ruthenium complex 3 is located in mitochondria and lysosomes, mostly in mitochondria, although both complexes entered A549 cells mainly through energy-dependent active transport. The nuclear morphological changes caused by Ir complex 1 were also detected by confocal microscopy. Ir complex 1 is more potent than cisplatin toward A549 and HeLa cells. DNA binding studies involved interaction with the nucleobases 9-ethylguanine, 9-methyladenine, ctDNA, and plasmid DNA. The determination of bovine serum albumin binding was also performed. Hydrolysis, stability, nucleobase binding, and catalytic NAD+/NADH hydride transfer tests for complexes 1 and 3 were also carried out. Both complexes activated depolarization of mitochondrial membrane potential and intracellular ROS overproduction and induced cell apoptosis. Complex 3 arrested the cell cycle at the G0/G1 phase by inactivation of CDK 4/cyclin D1. This work paves the way to track and monitor half-sandwich metal complexes in cells, shines a light on understanding their mechanism of action, and indicates their potential application as theranostic agents.

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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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Chiral, Porous, Hybrid Solids for Highly Enantioselective Heterogeneous Asymmetric Hydrogenation of beta-Keto Esters

Catalytic building blocks: Chiral porous zirconium phosphonates containing Rubinap moieties are synthesized by a molecular building-block approach, and characterized by a variety of techniques. These hybrid solids are used for enantioselective heterogeneous asymmetric hydrogenation of beta-keto esters with ee values of up to 95% (see picture). Ready tunability of such a molecular building-block approach promises to lead to useful heterogeneous asymmetric catalysts.

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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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Arene Ruthenium(II) Complexes as Low-Toxicity Inhibitor against the Proliferation, Migration, and Invasion of MDA-MB-231 Cells through Binding and Stabilizing c-myc G-Quadruplex DNA

Arene Ru(II) complexes have long been extensively studied as potential inhibitors against the proliferation of tumor cells, but their behavior against the migration and invasion of tumor cells needs further research. In this work, a series of arene Ru(II) complexes, (eta6-C6H6)Ru(p-XPIP)Cl]Cl (X = H, 1; F, 2; Cl, 3; Br, 4; and I, 5), have been synthesized, and their inhibitory activity against the migration and invasion of MDA-MB-231 breast cancer cells have been investigated. It is found that all of these complexes exhibit excellent inhibitory activity (IC50) against the growth of MDA-MB-231 breast cancer cells, and the value of IC50 for 1, 2, 3, 4, and 5 is about >300, 52.6, 11.4, 45.5, and 59.1 muM, respectively. Further studies by wound-healing assay, FITC-geltain assay, and flow cytometry assay showed that 3 can apparently suppress the migration and invasion of MDA-MB-231 cells via the joint action of S-phase arrest and apoptosis. Moreover, the binding behavior of these arene Ru(II) complexes with c-myc G-quadruplex DNA has also been studied, and the results showed that these complexes can bind and stabilize c-myc G-quadruplex DNA in groove binding mode. Also, the low toxicity of 3 was confirmed by its low inhibitory activity against the growth of normal MCF-10A breast cells in vitro and the development of zebrafish embryos in vivo. In other words, these results indicated that synthetic arene Ru(II) complexes can be developed as low-toxicity agents against the proliferation, migration, and invasion of breast cancer cells.

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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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Transition metal-catalyzed dehydrogenative germylation of olefins with tri-n-butylgermane

The catalyzed reaction of an excess of styrene with n-Bu3GeH using several ruthenium and rhodium complexes gave the corresponding vinylgermanes (alpha-trin-butylgermylstyrene, (Z)-beta-tri-n-butylgermylstyrene, and (E)-beta-tri-n-butylgermylstyrene), which are dehydrogenative germylation products. The most effective catalyst was RU3(CO)12, whose use resulted in selective formation of the vinylgermanes in high yields.

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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, SDS of cas: 37366-09-9

Arene-ruthenium complexes with phosphanylferrocenecarboxamides bearing polar hydroxyalkyl groups-synthesis, molecular structure, and catalytic use in redox isomerizations of allylic alcohols to carbonyl compounds

Phosphanylferrocenecarboxamide Ph2P-fc-CONHCH2CH 2OH (1, fc = ferrocene-1,1?-diyl) and its newly synthesized congeners, Ph2P-fc-CONHCH(CH2OH)2 (2) and Ph2P-fc-CONHC(CH2OH)3 (3), were converted to a series of (eta6-arene)ruthenium complexes [(eta6- arene)RuCl2(L-kappaP)] 5-7, where arene is benzene, p-cymene, and hexamethylbenzene and L = 1-3. All compounds were characterized by multinuclear NMR and IR spectroscopy, by mass spectrometry, and by elemental analysis. The molecular structures of 2, 3, 3O (a phosphane oxide resulting from the oxidation of 3), 5c¡¤CH2Cl2, and 6c¡¤Et2O were determined by single-crystal X-ray diffraction analysis. The ruthenium complexes were further evaluated as catalysts in the redox isomerization of allyl alcohols to carbonyl compounds. Complex [(eta6-p-cymene) RuCl2(1-kappaP)] (5b) proved to be a particularly attractive catalyst, being both readily available and catalytically active. Substrates with unsubstituted double bonds were cleanly isomerized with this catalyst in 1,2-dichloroethane (0.5 mol-% Ru, 80 C), whereas for those bearing substituents at the double bond (particularly in the position closer to the OH group) lower conversions and selectivities were achieved. A similar trend was noted when pure water was used as the solvent, except that the best results (complete conversion with 2 mol-% Ru) were seen for 1,3-diphenylallyl alcohol, the most hydrophobic substrate.

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