3-Sep-2021 News Some scientific research about Dichloro(benzene)ruthenium(II) dimer

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The cationic complexes [(eta6-arene)Ru(SC5H4NH)3]2+, arene being C6H6 (1), MeC6H5 (2), p-iPrC6H4Me (3) or C6Me6 (4), have been synthesised from the reaction of 4-pyridinethiol with the corresponding precursor (eta6-arene)2Ru2(mu2-Cl)2Cl2 and isolated as the chloride salts. The single-crystal X-ray structure of [4](PF6)2 reveals three 4-pyridinethiol moieties coordinated to the ruthenium centre through the sulphur atom, with the hydrogen atom transferred from the sulphur to the nitrogen atom. The electrochemical study of 1-4 shows a clear correlation between the Ru(II)/Ru(III) redox potentials and the number of alkyl substituents at the arene ligand (E? (RuII/III): 1 > 2 > 3 > 4), whereas the cytotoxicity towards A2780 ovarian cancer cells follows the series 4 > 1 > 3 > 2, the hexamethylbenzene derivative 4 being the most cytotoxic one. The corresponding reaction of the ortho-isomer, 2-pyridinethiol, with (eta6-C6Me6)2Ru2(mu2-Cl)2Cl2 does not lead to the expected 2-pyridinethiolato analogue, but yields the neutral complex (eta6-C6Me6)Ru(eta2-SC5H4N)(eta1-SC5H4N) (5). The analogous complex (eta6-C6Me6)Ru(eta2-SC9H6N)-(eta1-SC9H6N) (6) is obtained from the similar reaction with 2-quinolinethiol.

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

Sep 2021 News Can You Really Do Chemisty Experiments About Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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A new series of hexa-coordinated Ru(II) complexes of the type [Ru(L)(phen)2]X (1a?d) and [Ru(L)(bipy)2]X (2a?d) (where phen = 1,10-phenanthroline, bipy = 2,2?-bipyridine, X = NO3, BF4, ClO4, PF6) have been prepared by the reaction of (E)-2-(((5-((4-methoxyphenyl)ethynyl)pyridin-2-yl)imino)methyl)-4-((4-nitrophenyl)ethynyl)phenol (L) with [Ru(phen)2]Cl2·2H2O and [Ru(bipy)2]Cl2·2H2O. The complexes were characterized by physico-chemical and spectroscopic methods. All complexes are 1:1 conducting and diamagnetic in nature. In acetonitrile solution, the complexes displayed one reversible Ru(II)?Ru(III) oxidation couple and one irreversible Ru(III)?Ru(IV) oxidation and are sensitive to pi-acidic character of phen and bipy ligands. The complexes show room-temperature luminescence originated from the lowest energy metal-to-ligand charge transfer excited state and are sensitive to difference in size of the counter anions. All the complexes displayed second harmonic generation by Kurtz-powder technique indicating their potential for the application as a useful NLO material.

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

Sep 2021 News A new application about Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II), molecular formula is C20H16Cl2N4Ru, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 15746-57-3, Product Details of 15746-57-3

A functional ruthenium(II) complex that can act as a probe for response to hypochlorous acid (HOCl) in aqueous media with photoluminescence (PL) and electrochemiluminescence (ECL) dual-signals, [Ru(bpy)2(DB-phen)](PF6)2 [bpy: 2,2?-bipyridine; DB-phen: 5-(2,4-dimethoxybenzylamino)-1,10-phenanthroline)], has been designed and synthesized. The complex is highly luminescent both under the light excitation and the electrochemical induction. It can specifically react with HOCl in physiological pH aqueous media to afford its chlorinated derivative, [Ru(bpy)2(DBCA-phen)](PF6)2 [DBCA-phen: 5-(2,4-dimethoxybenzyl-chloroamino)-1,10-phenanthroline], accompanied by remarkable decreases in its PL and ECL intensities. The PL and ECL abatements of [Ru(bpy)2(DB-phen)](PF6)2 show good linear correlation to the concentration of HOCl with detection limits at low micromolar concentration level, and the PL and ECL responses of the complex to HOCl are highly specific without interferences of other reactive oxygen/nitrogen species. These features enabled [Ru(bpy)2(DB-phen)](PF6)2 to be used as a probe for the highly selective and sensitive detection of HOCl in aqueous media with PL and ECL dual-modes.

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

02/9/2021 News Archives for Chemistry Experiments of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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The reaction between Ru(bpy)(2)Cl(2) (bpy=2,2′-bipyridine) and di-2-pyridylketone-p-nitrophenylhydrazone (dpknph) in refluxing ethanol gave [Ru(bpy)(2)(dpknph)]Cl(2) in good yield. Optical measurements on [Ru(bpy)(2)(dpknph)]Cl(2) in non-aqueous media revealed the presence of two interlocked electronic states due to conformational changes associated with the hydrazone moiety of [Ru(bpy)(2)(dpknph)]Cl(2). The equilibrium distribution of the high-energy beta-conformation associated with the high-energy electronic state and the low-energy alpha-conformation associated with the low-energy electronic state is solvent and solute dependent controlled by the solvent-solute and solute-solute interactions. The interplay between the alpha- and beta-conformations of [Ru(bpy)(2)(dpknph)]Cl(2) allowed calculations of the extinction coefficients of electronic states by forcing the equilibrium to shift to one conformation using chemical stimuli. Extinction coefficients of 56000+/-2000 and 48500+/-2000 M(-1) cm(-1) were calculated in DMSO for the beta- and alpha-conformations of [Ru(bpy)(2)(dpknph)]Cl(2), respectively, using excess HgCl(2) in DMSO. Thermo-optical measurements on [Ru(bpy)(2)(dpknph)]Cl(2) in DMSO confirmed the interconversion between the alpha- and beta-conformations of [Ru(bpy)(2)(dpknph)]Cl(2) and gave changes in enthalpy (DeltaH(o)) of -35.5+/-4.0 and 13.0+/-0.5 kJ mol(-1), entropy (DeltaS(o)) of -126.9+/-20 and 45.2+/-4.5 kJ mol(-1), and free energy (DeltaG(o)) of 2.31+/-0.2 and -0.48+/-0.2 kJ mol(-1) in the absence and presence of NaBH(4) at 295 K. The high values for the extinction coefficients and low values and sensitivity of the activation parameters for the interconversion between the alpha- and beta-conformations of [Ru(bpy)(2)(dpknph)]Cl(2) in DMSO to solution composition allowed for the use of this system ([Ru(bpy)(2)(dpknph)]Cl(2) and surrounding solvent or solute molecules) as a spectrophotometric sensor for a variety of chemical stimuli that include metal ions. Group 12 metal ions in concentrations as low as 1.00×10(-8) M can be detected and determined using [Ru(bpy)(2)(dpknph)]Cl(2) in DMSO in the presence and absence of NaBH(4).

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

02/9/2021 News Extracurricular laboratory:new discovery of Dichloro(benzene)ruthenium(II) dimer

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The reaction of [Rh(mu-SH)(CO)(PPh3)]2 or [Rh(mu-SH){P(OPh)3}2]2 with [Cp*MCl2]2 (M = Rh, Ir) in the presence of NEt 3 afforded the Rh3 and IrRh2 sulfido-bridged compounds [Cp*M(mu3-S)2Rh2(CO) 2(PPh3)2] (M = Rh, 1; Ir, 2) and [Cp*Rh(mu3-S)2Rh2{P(OPh) 3}4] (3). The reaction with [MCl2(cod)] (M = Pd, Pt), cis-[PtCl2(PPh3)2] or [(eta6-C6H6)RuCl2]2 under the same experimental conditions gave [(cod)M(mu3-S) 2Rh2{P(OPh)3}4] (M = Pd, 6; Pt, 7), [(cod)M(mu3-S)2Rh2(CO)2(PPh 3)2] (M = Pd, 8; Pt, 9), [(PPh3) 2Pt(mu3-S)2Rh2(CO) 2(PPh3)2] (10) and [(eta6-C 6H6)Ru(mu3-S)2Rh 2(CO)2(PPh3)2] (12), with PdRh 2, PtRh2 and RuRh2 trimetallic cores. The aggregates derived from [Rh(mu-SH)(CO)(PPh3)]2 were isolated as a mixture of trans and cis isomers in which the trans isomer predominates. The reaction of [Rh(mu-SH){P(OPh)3}2] 2 with 2 equiv. of n-BuLi at 253 K followed by addition of [Cp*IrCl2]2 gave [Cp*Ir(mu3-S) 2Rh2{P(OPh)3}4] (4) and [Cp*2ClIr2(mu3-S)2Rh{P(OPh) 3}2] (5) in a 3:::2 ratio. The RuRh2 compound [(eta6-C6H6)Ru(mu3-S) 2Rh2{P(OPh)3}4] (11) was prepared similarly from [Rh(mu-SH){P(OPh)3}2]2 and [(eta6-C6H6)RuCl2]2 using n-BuLi as a deprotonating agent. The molecular structures of compounds 3, 6, 7, 9 and 11 have been determined by X-ray analysis. The trinuclear complexes exhibit an asymmetric triangular metal core with two triply bridging sulfido ligands resulting in a distorted trigonal-bipyramidal M3(mu 3-S)2 heterometallic metal-sulfur core.

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

2-Sep-2021 News Extended knowledge of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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In an article, published in an article, once mentioned the application of 15746-57-3, Name is Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II),molecular formula is C20H16Cl2N4Ru, is a conventional compound. this article was the specific content is as follows.category: ruthenium-catalysts

We report two ruthenium(II) polypyridyl complexes with pendant phenol/catechol functionality that act as colorimetric sensors for fluoride ions. Experiments have revealed that hydrogen bond formation occurs with a slight excess of fluoride ion. However, in higher [F-], deprotonation of the O-H functionality resulted. Time-dependent (TD-DFT) calculations at the B3LYP/LANL2DZ level have shown that new bands appear at longer wavelengths upon complexation with fluoride ions. These are of mixed character, MLCT (dpi(Ru) ? pi*(Li/bpy)), and intra- and interligand [pi(L 1) ? pi*(bpy) and pi(L1) ? pi*(L1)] transitions. These complexes also act as sensors for fluoride ions in solvent-water mixtures.

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

2-Sep-2021 News Final Thoughts on Chemistry for Dichloro(benzene)ruthenium(II) dimer

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Reactions of 3,6-bis(2-pyridyl)-4-phenylpyridazine (Lph) with [(eta6-arene)Ru(mu-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me and C6Me6), [(eta5-C5Me5)M(mu-Cl)Cl]2, (M = Rh and Ir) and [(eta5-Cp)Ru(PPh3)2Cl] (Cp = C5H5, C5Me5 and C9H7) afford mononuclear complexes of the type [(eta6-arene)Ru(Lph)Cl]PF6, [(eta5-C5Me5)M(Lph)Cl]PF6 and [(Cp)Ru(Lph)(PPh3)]PF6 with different structural motifs depending on the pi-acidity of the ligand, electronic properties of the central metal atom and nature of the co-ligands. Complexes [(eta6-C6H6)Ru(Lph)Cl]PF6 1, [(eta6-p-iPrC6H4Me)Ru(Lph)Cl]PF6 2, [(eta5-C5Me5)Ir(Lph)Cl]PF6 5, [(eta5-Cp)Ru(PPh3)(Lph)]PF6, (Cp = C5H5, 6; C5Me5, 7; C9H7, 8) show the type-A binding mode (see text), while complexes [(eta6-C6Me6)Ru(Lph)Cl]PF6 3 and [(eta5-C5Me5)Rh(Lph)Cl]PF6 4 show the type-B binding mode (see text). These differences reflect the more electron-rich character of the [(eta6-C6Me6)Ru(mu-Cl)Cl]2 and [(eta5-C5Me5)Rh(mu-Cl)Cl]2 complexes compared to the other starting precursor complexes. Binding modes of the ligand Lph are determined by 1H NMR spectroscopy, single-crystal X-ray analysis as well as evidence obtained from the solid-state structures and corroborated by density functional theory calculations. From the systems studied here, it is concluded that the electron density on the central metal atom of these complexes plays an important role in deciding the ligand binding sites.

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

2-Sep-2021 News Archives for Chemistry Experiments of Dichloro(benzene)ruthenium(II) dimer

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Ru(ii) polypyridine complexes which can undergo photo-induced ligand dissociation and subsequent DNA covalent binding may potentially serve as photoactivated chemotherapeutic (PACT) agents. In this paper, three fluorinated dppz ligand coordinated Ru(ii) complexes (2-4) containing four monodentate pyridine ligands were studied. All complexes released one pyridine and covalently bound to DNA upon 470 nm irradiation. Compared with the parent complex [Ru(dppz)(py)4]2+ (1), 2-4 displayed enhanced phototoxicity but diminished dark cytotoxicity, more favorable for PACT application. Complex 3 is the most efficient one with IC50 values of about 8 muM toward HeLa and SKOV-3 cell lines, and also has a much higher IC50 value toward normal L-02 cells. Our results indicate that fluorination on the retaining ligand may be an efficient way to improve the drug activity of Ru(ii) PACT agents.

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

2-Sep-2021 News New explortion of Dichloro(benzene)ruthenium(II) dimer

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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

A variety of planar chiral Ru-complexes bearing tropos ortho-substituted biphenyl ligands were synthesized. The planar chirality control of the Ru complexes by enantiopure (R)-H8DABN selectively gave the thermodynamically stable diastereomers via association of solvents employed. Copyright

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

Sep 2021 News More research is needed about Dichloro(benzene)ruthenium(II) dimer

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The invention provides a method for preparing nitrile compounds through ruthenium metal complex catalytic primary amine dehydrogenation, and belongs to the technical field of energy and homogeneous catalysis. The invention successfully designs a series of ruthenium metal complex catalysts, and can efficiently catalyze the dehydrogenation of primary amine compounds to prepare nitrile compounds. The catalyst has the advantages of simple preparation method, good stability, high selectivity and wide substrate applicability. Taking benzylamine dehydrogenation to give a nitrile as an example, the yield of benzonitrile can reach unitz 95%. This reaction does not need to use highly toxic cyanogen reagent and strong oxidant, has avoided causing the pollution to the environment, has also eliminated the potential safety hazard. The only by-product of this catalytic reaction is hydrogen, and it both can regard as green energy, also can regard as the hydrogen source of other reaction. In addition, the realization of the catalytic reaction also provides an idea for the amine substances as the liquid hydrogen storage material. (by machine translation)

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