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Selective reduction of 2-nitro-3-methoxybenzaldehyde provides 2-amino-3-methoxybenzaldehyde that undergoes the Friedlaender condensation with a variety of acetyl-substituted derivatives of pyridine and 1,10-phenanthroline. After cleavage of the methyl ether, the resulting polydentate analogues of 8-hydroxyquinoline are excellent ligands for ruthenium. The resulting oxidation state of the metal center depends on the anionic character of the ligands. The presence of two electron donating anionic ligands results in a Ru(III) complex as evidenced by paramagnetic NMR behavior. The electronic absorption and redox properties of the complexes were measured and found to be consistent with the anionic character of the 8-HQ moieties. A planar pentadentate ligand provides two Ru-O and two Ru-N bonds in the equatorial plane. An X-ray structure shows that the central pyridine of the ligand is oriented toward the metal but held at a distance of 2.44 A.

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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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Polypyridyl ruthenium complexes have been intensively investigated for their remarkable antiproliferative properties and some are currently being tested in clinical trials. Here, we investigated the impact of illumination on the biological properties of a series of new cyclometalated ruthenium compounds with increased pi-conjugation. We determined that various of these complexes display a bivalent biological activity as they are highly cytotoxic by themselves in absence of light while their cytotoxicity can significantly be elevated towards an IC50 in the nanomolar range upon illumination. In particular, we showed that these complexes are particularly active (IC50 < 1 muM) on two gastric cancer cell lines (AGS, KATO III) that are resistant towards cisplatin (IC50 > 25 muM). As expected, light activation leads to increased production of singlet oxygen species in vitro and accumulation of reactive oxygen species in vivo. Importantly, we established that light exposure shifts the mode of action of the complexes towards activation of a caspase 3-dependent apoptosis that correlates with increased DNA damage. Altogether, this study characterizes novel ruthenium complexes with dual activity that can be tuned towards different mode of action in order to bypass cancer cell resistance mechanisms.

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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 process for the preparation of an enantiomerically enriched chiral amine of formula (10), or the opposite enantiomer thereof, from an imine of formula (11) wherein (i) R1 is aryl, R2 is alkyl and R3 is aryl or aryl-CH2-, or (iii) R2 is linked with R1 and/or R3 to form one or more rings and R3 or R1 (if not in a ring) is H or a non-interfering organic group, the number of C atoms in each of R1, R2 and R3 being up to 30, comprises asymetric hydrogenation of the imine in the presence of a base and, as catalyst, a ruthenium complex of a chiral diphosphine and a chiral diamine.

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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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Figure Presented Radically complex: Well-defined mononuclear RuI and OsI complexes (see scheme) have metalloradical character, as indicated by EPR spectroscopy and DFT calculations. The RuI and OsI metalloradicals exhibit both one-electron and two-electron redox reactivity. The latter process affords unusual imido complexes with substantial radical character on the {ArN} moiety.

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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 present invention pertains to a method for producing an optically active compound which includes a step for reducing an imino group of an imine compound or a step for reducing an unsaturated bond of a heterocyclic compound, while in the presence of hydrogen gas as a hydrogen donor and one or more types of complexes selected from a group consisting of a complex represented by general formula (1), a complex represented by general formula (2), a complex represented by general formula (3), and a complex represented by general formula (4) (the general formulas (1)-(4) are as stipulated by claim 1).

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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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Bio-derived furans such as 2-furfural (furfural), 5-hydroxymethyl-2-furfural (5-HMF) and 5-methyl-2-furfural (5-MF) were successfully transformed to a ketoacid, levulinic acid (LA), and diketones, 1-hydroxyhexane-2,5-dione (1-HHD), 3-hydroxyhexane-2,5-dione (3-HHD) and hexane-2,5-dione (HD), under moderate reaction conditions using water soluble and recyclable 8-aminoquinoline coordinated arene-ruthenium(ii) complexes. Under the optimized reaction conditions using 1 mol% catalyst in the presence of 12 equivalents of formic acid at 80-100 C, complete conversion of furfural to LA with high selectivity was achieved. Several experiments along with 1H NMR spectral studies are described which provide more insights into the mechanism underlying the transformation of furans to open ring components. Experiments performed using structural analogues of the active catalyst inferred a structure-activity relationship for the observed superior catalytic activity of the 8-aminoquinoline coordinated arene-ruthenium(ii) complex. Furthermore, due to the high aqueous solubility of the studied complexes, high recyclability, up to 4 catalytic runs, was achieved without any significant loss of activity. Molecular identities of the studied 8-aminoquinoline coordinated arene-ruthenium(ii) complex were also confirmed using single-crystal X-ray diffraction studies.

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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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Reaction of furan and thiophen with an alcohol (R-OH) at 140 deg C, using a ruthenium catalyst, affords the R-alkylated dimers (2) and R,R-dialkylated trimers (3) of furan and of thiophene along with gamma-keto esters (4).

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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 composition comprising dihydropyrazinyl anions that can be coordinated as 6 electron ligands to a broad range of different metals to yield volatile metal complexes for ALD and CVD depositions are described herein. Also described herein are undeprotonated dihydropyrazines that can coordinate to metals as stabilizing neutral ligands. In one embodiment, the composition is used for the direct liquid injection delivery of the metal dihydropyrazinyl complex precursor to the chamber of an ALD or CVD chamber for the deposition of metal-containing thin films such as, for example, ruthenium or cobalt metal films.

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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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Abstract: The new water soluble chiral Ru(II)-benzene complexes of the type [RuCl 2(eta6-C 6H 6) L] were obtained from the reactions between [RuCl2(eta6-C6H6)]2 and the chiral aroylthiourea ligands (L) derived from unprotected D/L-alanine and characterized. The solid-state structure of representative complexes was confirmed by single crystal X-ray diffraction technique. The Ru(II)-benzene complexes catalyzed the asymmetric transfer hydrogenation (ATH) of aromatic ketones to their enantiopure secondary alcohols. The reactions were carried out in the presence of formic acid?triethylamine mixture in water, and the product alcohols were obtained with excellent conversions (up to 99%) and enantiomeric excesses (up to 99%). The scope of the catalytic system was extended to various aromatic ketones. The catalytic activity of the present water-soluble Ru-benzene complexes toward enantioselective reduction of ketones was considerably higher than that of p-cymene analogues in water. Graphical Abstract: The water-soluble chiral Ru(II)-benzene complexes were produced from the reactions between [RuCl2(eta6-C6H6)]2 and the chiral aroylthiourea ligands derived from unprotected D/L-alanine. The catalytic activity of the Ru(II)-benzene complexes toward enantioselective reduction of ketones was found to be good in water medium.[Figure not available: see fulltext.].

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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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(Figure Presented) Alkane and arene join together: Various arenes were coupled directly with simple cycloalkanes. The reaction was catalyzed by ruthenium under oxidative conditions to give substituted cycloalkylarenes regioselectively (see scheme).

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