Category: 37366-09-9

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Monocationic mu-diborolyl triple-decker complexes [CpCo(mu-1,3-C 3B2Me5)M(ring)]+: Synthesis, structures, and electrochemistry

Cationic triple-decker complexes with a bridging diborolyl ligand, [CpCo(mu-1,3-C3B2Me5)M(ring)]+ (M(ring) = CoCp (2a), CoCp* (2b), RhCp (3a), RhCp* (3b), IrCp (4a), IrCp* (4b), Ru(C6H6) (5a), Ru(p-MeC 6H4Pri) (5b), Ru(C6Me6) (5c), Ru(eta6-cycloheptatriene) (6)), were synthesized by reaction of CpCo(mu-1,3-C3B2Me5)Tl with [M(ring)Hal2]2. The structures of 2aBPh4, 2bPF6, 4aPF6, 5aOTf, and 5cPF6 were determined by X-ray diffraction. The electron-transfer ability of the complexes has been ascertained by electrochemical and spectroelectrochemical techniques. In general, they are able to shuttle reversibly in the sequence 2+/+/0/-, plausibly affording completely delocalized mixed-valence derivatives. DFT calculations revealed structural changes accompanying redox processes and satisfactorily predicted the potentials for the first reduction and first oxidation.

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

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, Formula: C12H12Cl4Ru2

Facile entry to germanate and stannate complexes [(eta6-arene)RuCl(eta2-dppm)]+[ECl3]- (E = Ge, Sn) as potent anti-cancer agents

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

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Two efficient enantioselective syntheses of 2-amino-1-phenylethanol

Two enantioselective methods for the synthesis of 2-amino-1-phenylethanol have been developed. The first utilizes an enantioselective oxazaborolidine- catalyzed borane reduction of 2-chloroacetophenone (phenacyl chloride) to give the chiral chloro alcohol in good yield with an ee in the 93-97% range. Reaction with dilute ammonium hydroxide produced the amino alcohol in good yield with a high ee. The second approach involved first the conversion of phenacyl chloride to the succinimido acetophenone which was then hydrogenated using a chiral ruthenium complex in conjunction with a base and an optically active amine (Noyori procedure). This gave the optically active succinimido alcohol in very good yield with an ee of 98%. Hydrolysis with dilute base produced the optically active amino alcohol in very good yield and excellent enantioselectivity.

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

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A novel nitrogen-containing ligand ruthenium complex and its preparation and use (by machine translation)

The present invention relates to a new metal ruthenium complex having glyphosate and nitrogen ligands, the preparation method therefor, and uses thereof. Provided is a transition metal complex of a new structure having glyphosate ligand and nitrogen ligand having a structural characteristic of NH2-N(sp2). The overall structural formula (I) of the metal ruthenium complex is: [RuLmL’ChiUpsilon], where X and Y can be identical or different. X can be chlorine, bromine, iodine, or hydrogen, and Y can be chlorine, bromine, iodine, or BetaH4. Also disclosed are a preparation method for and uses of the transition metal complex. The metal ruthenium complex and the nitrogen ligand mentioned in the present invention are easy to synthesize and can be used in catalytic asymmetric hydrogenation reactions, in particular in catalytic asymmetric hydrogenation reactions of ketones having aryl or unsaturated alkyl at the alpha position, diaryl ketone and analogues thereof, ketones having tert-alkyl at the alpha position, ketones having a heteroatomic group at the alpha position, beta-Nu, Nu-dimethylamino-alpha-acetophenone and derivatives thereof, and other aryl-alkyl ketone compounds. When the metal ruthenium complex is used for catalytic hydrogenation of a ketone, the metal complex can be prepared in-situ.

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

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Asymmetric Synthesis of Chiral Primary Amines by Ruthenium-Catalyzed Direct Reductive Amination of Alkyl Aryl Ketones with Ammonium Salts and Molecular H2

A ruthenium/C3-TunePhos catalytic system has been identified for highly efficient direct reductive amination of simple ketones. The strategy makes use of ammonium acetate as the amine source and H2 as the reductant and is a user-friendly and operatively simple access to industrially relevant primary amines. Excellent enantiocontrol (>90% ee for most cases) was achieved with a wide range of alkyl aryl ketones. The practicability of this methodology has been highlighted by scalable synthesis of key intermediates of three drug molecules. Moreover, an improved synthetic route to the optimal diphosphine ligand C3-TunePhos is also presented.

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

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Unsolvated ruthenium(II) benzene dichloride: The beta polymorph

A novel polymorph of the unsolvated species [Ru2(benzene) 2Cl4] (beta form in the following) was serendipitously isolated as a polycrystalline powder. Its molecular and crystal structure was unraveled by means of state-of-the-art X-ray powder diffraction structure determination methods applied to laboratory data, and was compared to those of both the alpha polymorph and the CHCl3 solvate, throwing light on some discrepant results recently appeared in the literature. The thermal behavior of the alpha and beta polymorphs was investigated by coupling thermogravimetric analyses to variable-temperature X-ray powder diffraction experiments. No temperature-stimulated phase transformation could be detected between the two polymorphs, each preserving its structural features up to decomposition, suggesting that kinetic, more than thermodynamic, factors regulate their isolation.

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

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, category: ruthenium-catalysts

Pyridylphosphinate metal complexes: Synthesis, structural characterisation and biological activity

For the first time, a series of 25 pseudo-octahedral pyridylphosphinate metal complexes (Ru, Os, Rh, Ir) has been synthesised and assessed in biological systems. Each metal complex incorporates a pyridylphosphinate ligand, a monodentate halide and a capping eta6-bound aromatic ligand. Solid- and solution-state analyses of two complexes reveal a structural preference for one of a possible two diastereomers. The metal chlorides hydrolyse rapidly in D2O to form a 1:1 equilibrium ratio between the aqua and chloride adducts. The pKa of the aqua adduct depends upon the pyridyl substituent and the metal but has little dependence upon the phosphinate R? group. Toxicity was measured in vitro against non-small cell lung carcinoma H460 cells, with the most potent complexes reporting IC50 values around 50 muM. Binding studies with selected amino acids and nucleobases provide a rationale for the variation in toxicity observed within the series. Finally, an investigation into the ability of the chelating amino acid l-His to displace the phosphinate O-metal bond shows the potential for phosphinate complexes to act as prodrugs that can be activated in the intracellular environment.

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

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, Computed Properties of C12H12Cl4Ru2

Arene ruthenium complexes as versatile catalysts in water in both transfer hydrogenation of ketones and oxidation of alcohols. Selective deuterium labeling of rac-1-phenylethanol

The preparation of three series of arene Ru(II) half-sandwich compounds with the functional ligand 4,4?-dimethoxy-2,2?-bipyridine (dmobpy) is described. The new cationic derivatives have the general formula [(eta6-arene)RuCl(kappa2-N,N-dmobpy)]X (arene = benzene, X = Cl- ([1]Cl), BF4- ([1][BF 4]), TsO- ([1]TsO), PF6- ([1][PF6]); arene = p-cymene (p-cym), X = Cl- ([2]Cl), BF4- ([2][BF4]), TsO- ([2]TsO), PF6- ([2][PF6]); arene = 2-phenoxy-1-ethanol (phoxet), X = Cl- ([3]Cl), BF4- ([3][BF 4]), TsO- ([3]TsO), PF6- ([3][PF6])). The structures of [1]Cl, [1]TsO, [2]TsO, [2][BF 4], and [2][PF6] were determined by X-ray crystallography. All of the complexes except the PF6- salts were water-soluble, and they behaved as active catalysts in two different processes: the transfer hydrogenation of water-soluble and -insoluble ketones to the corresponding alcohols, using HCOONa as the hydrogen source at pH 4, and the oxidation of rac-1-phenylethanol to acetophenone with tBuOOH at pH 7, both in aqueous solution. For the transfer hydrogenation with p-cymene complexes the aqua, formato, and hydride species were detected by means of 1H NMR experiments in D2O. It was found that the cationic hydrido complex was [(eta6-p-cymene)RuD(dmobpy)]+. The reversible and pH-dependent formation of the hydroxo derivative was also observed. When the catalytic transfer hydrogenation was performed in D 2O, the 1-phenylethanol obtained was selectively deuterated at the benzylic carbon. Mechanistic proposals are also included.

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

Electric Literature of 37366-09-9, Catalysts are substances that increase the reaction rate of a chemical reaction without being consumed in the process. 37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2. In a Article£¬once mentioned of 37366-09-9

Diaminohexopyranosides as ligands in half-sandwich ruthenium(II), rhodium(III), and iridium(III) complexes

The syntheses of methyl 2,3-diamino-4,6-O-benzylidene-2,3-dideoxy-alpha-d-hexopyranosides of glucose, mannose, gulose, and talose and methyl 2-amino-4,6-benzylidene-2,3-dideoxy-3-tosylamido-alpha-d-glucopyranoside are exhaustively presented, as well as their application as ligands in half-sandwich ruthenium(II), rhodium(III), and iridium(III) complexes. The complex formation occurs highly diastereoselectively, creating a stereogenic metal center. The molecular structures of the ligands and their complexes were investigated by X-ray structure analysis, NMR spectroscopy, polarimetry, and DFT methods. The diamino monosaccharide complexes have been subjected to antitumor activity studies. In vitro tests of a few ruthenium complexes against different cancer cell types showed antiproliferative activities 4-10 times lower than that of cisplatin.

The proportionality constant is the rate constant for the particular unimolecular reaction. the reaction rate is directly proportional to the concentration of the reactant. I hope my blog about 37366-09-9 is helpful to your research., Electric Literature of 37366-09-9

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

Reference of 37366-09-9, An article , which mentions 37366-09-9, molecular formula is C12H12Cl4Ru2. The compound – Dichloro(benzene)ruthenium(II) dimer played an important role in people’s production and life.

Role of the Trichlorostannyl Ligand in Tin?Ruthenium Arene Complexes: Experimental and Computational Studies

A set of neutral and ionic ruthenium arene trichlorostannyl complexes are reported herein. The tin(II) compounds L1SnCl {1; L1 = [2-(CH2NEt2)-4,6-(tBu)2C6H2]?} and [L2SnCl][SnCl3] {2; L2 = 2,6-[(CH3)C=N(C6H3-2,6-iPr2)2]C5H3N} showed a rather different reactivity towards the ruthenium complex [(eta6-cymene)RuCl]2(eta-Cl)2. As a consequence, the neutral complex [Ru(eta6-cymene)(L1SnCl)Cl2] (4) and the ionic compound [L2SnCl][Ru(eta6-cymene)(SnCl3)2Cl] (8) were isolated. The insertion reaction of 4 with SnCl2 provided the neutral trimetallic ruthenium complex [Ru(eta6-cymene)(L1SnCl)(SnCl3)Cl] (6). Analogous ruthenium complexes [Ru(eta6-cymene)(L3PPh2)Cl2] (5) and [Ru(eta6-cymene)(L3PPh2)(SnCl3)Cl] (7) containing the phosphane ligand L3PPh2 {3; L3 = [2,6-iPr2-(C6H3)NH]?} were also prepared to evaluate the donor?acceptor strength of the tin(II)- and phosphorus-containing ligands. The structural characterization and DFT calculations of the above-mentioned complexes suggest a strong influence of the [SnCl3]? moiety on the Ru?E interaction (E = Sn, P). The influence of the trichlorostannyl ligand on the Ru?E interaction in the complexes 4?7 was further evaluated by means of a distortion/interaction analysis.

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