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A series of new N-heterocyclic carbene (NHC)eRu(II) complexes functionalized with additional hemilabile donor groups, such as a hydroxy-amide group, were successfully synthesized and structurally characterized. Preliminary studies indicated that the complexes acted as precatalysts with moderate activity in the asymmetric transfer hydrogenation at room temperature without temperature control. The investigation of the effect of varying the eta6-arene ligands showed that these ligands appeared to significantly alter the activity of the complexes as precatalysts. Furthermore, it was revealed that the hydroxy functional group on the NHC ligand side-arm not only induced the stereoselectivity of the reaction but also enhanced the reaction rate.

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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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Reactions of the dinuclear complexes [(eta6-arene)Ru(mu-Cl)Cl]2 (arene = C6H6, p-iPrC6H4Me) and [(eta5-C5Me5)M(mu-Cl)Cl]2 (M = Rh, Ir) with 2-substituted-1,8-naphthyridine ligands, 2-(2-pyridyl)-1,8-naphthyridine (pyNp), 2-(2-thiazolyl)-1,8-naphthyridine (tzNp) and 2-(2-furyl)-1,8-naphthyridine (fuNp), lead to the formation of the mononuclear cationic complexes [(eta6-C6H6)Ru(L)Cl]+ {L = pyNp (1); tzNp (2); fuNp (3)}, [(eta6-p-iPrC6H4Me)Ru(L)Cl]+ {L = pyNp (4); tzNp (5); fuNp (6)}, [(eta5-C5Me5)Rh(L)Cl]+ {L = pyNp (7); tzNp (8); fuNp (9)} and [(eta5-C5Me5)Ir(L)Cl]+ {L = pyNp (10); tzNp (11); fuNp (12)}. All these complexes are isolated as chloro or hexafluorophosphate salts and characterized by IR, NMR, mass spectrometry and UV/Vis spectroscopy. The molecular structures of [1]Cl, [2]PF6, [4]PF6, [5]PF6 and [10]PF6 have been established by single crystal X-ray structure analysis.

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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 family of {Ru(arene)}2+-containing heteropolytungstates of general formula [{Ru(L)}2(alpha-XW11O39) 2WO2]m- (L = benzene, p-cymene; X = Ge IV, SiIV, m = 10; X = BIII, m = 12) has been prepared in aqueous acidic medium (pH ? 4). The 1:1 interaction of [Ru(C 6H6)Cl2]2 or [Ru(p-cymene)Cl 2]2 with [beta2-GeW11O 39]8- led to the formation of [{Ru(benzene)} 2(GeW11O39)2WO2] 10- (1) and [{Ru(p-cymene)}2(GeW11O 39)2WO2]10- (2), respectively. Replacing [beta2-GeW11O39]8- by [alpha-SiW11O39]8- resulted in [{Ru(benzene)}2(SiW11O39)2WO 2]10- (3) and [{Ru(p-cymene)}2(SiW 11O39)2WO2][SiW12O 40]0.512- (4), respectively. The reaction of [alpha-HBW11O39]8- with the respective {Ru(arene)}2+-containing precursors resulted in polyanions [{Ru(benzene)}2(HBW11O39)2WO 2]10- (5) and [{Ru(p-cymene)}2(HBW 11O39)2WO2]10- (6), respectively. Single-crystal XRD analysis of the hydrated salts of 1-6 revealed that these species comprise two Keggin fragments, [{Ru(L)}alpha-XW 11O39]6- (L = benzene, p-cymene; X = Ge IV, SiIV) for polyanions 1-4 and [{Ru(L)}alpha-HBW 11O39]6- (L = benzene, p-cymene) for 5 and 6, connected via a cis-dioxo {WO2}2+ unit. In addition, the heteropolytungstates were characterized by thermogravimetric analysis, IR spectroscopy, elemental analysis, and solution electrochemical studies. Copyright

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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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Highly enantioselective tandem hydrogenation/lactonization of various 2-acylarylcarboxylates including 2-aroylarylcarboxylates were realized by using [RuCl(benzene)(S)-SunPhos]Cl as the catalyst under mild reaction conditions. Excellent enantioselectivities (up to 99.6 % ee) and activities (S/C=1000) were obtained. This convenient and practical method enables a direct access to a series of highly optically pure 3-substituted phthalides that are very important molecules as valuable pharmacological compounds and diversified synthons for medicinal chemistry. Moreover, a gram-scale reaction was performed to further demonstrate the practicality of this approach.

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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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37366-09-9, Name is Dichloro(benzene)ruthenium(II) dimer, molecular formula is C12H12Cl4Ru2, belongs to ruthenium-catalysts compound, is a common compound. In a patnet, once mentioned the new application about 37366-09-9, Product Details of 37366-09-9

New water-soluble complexes [(eta6-C6H6)RuCl(C5H4N-2-CH = N-R)]Cl (1) (with R = 4-hydroxymethylphenyl (a), 2,4-dichlorophenyl (b), 2-fluorophenyl (c), 3-carboxyphenyl (d)) have been synthesized by reacting [(eta6-C6H6)Ru(mu-Cl)Cl]2 with the N,N?-bidentate ligands in a 1:2 ratio. Full characterization of all complexes was accomplished using 1H and 13C NMR, elemental analyses, UV-Vis spectroscopy, IR spectroscopy and single crystal X-ray crystallography for determination of the structure of 1d, as 1d·4H2O. The single crystal structure confirmed coordination of the ligand to the ruthenium(II) center leading to a structure commonly described as a pseudo-octahedral, three-legged piano stool. The geometry around the Ru(II) center is such that the arene ring occupies the apex of the stool while the N,N?-bidentate ligand and a chloride occupy the base of the stool. The synthesized Ru(II) complexes were tested as catalysts for oxidation of styrene using NaIO4 as a co-oxidant in a biphasic system. All complexes were active, giving good yields of benzaldehyde. Catalyst 1c was later investigated for olefin oxidation and gave high yields of the corresponding aldehydes as the major products in all cases.

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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 series of neutral RuII half-sandwich complexes of the type [(eta6-arene)Ru(N,N?)Cl] where the arene is para-cymene (p-cym), hexamethylbenzene (hmb), biphenyl (bip), or benzene (bn) and N,N? is N-(2-aminoethyl)-4-(trifluoromethyl)benzenesulfonamide (TfEn), N-(2-aminoethyl)-4-toluenesulfonamide (TsEn), or N-(2-aminoethyl) methylenesulfonamide (MsEn) were synthesized and characterized. X-ray crystal structures of [(p-cym)Ru(MsEn)Cl] (1), [(hmb)Ru(TsEn)Cl] (5), [(hmb)Ru(TfEn)Cl] (6), [(bip)Ru(MsEn)Cl] (7), and [(bip)Ru(TsEn)Cl] (8) have been determined. The complexes can regioselectively catalyze the transfer hydrogenation of NAD + to give 1,4-NADH in the presence of formate. The turnover frequencies (TOF) when the arene is varied decrease in the order bn > bip > p-cym > hmb for complexes with the same N,N? chelating ligand. The TOF decreased with variation in the N,N? chelating ligand in the order TfEn > TsEn > MsEn for a given arene. [(bn)Ru(TfEn)Cl] (12) was the most active, with a TOF of 10.4 h-1. The effects of NAD+ and formate concentration on the reaction rates were determined for [(p-cym)Ru(TsEn)Cl] (2). Isotope studies implicated the formation of [(arene)Ru(N,N?)(H)] as the rate-limiting step. The coordination of formate and subsequent CO2 elimination to generate the hydride were modeled computationally by density functional theory (DFT). CO2 elimination occurs via a two-step process with the coordinated formate first twisting to present its hydrogen toward the metal center. The computed barriers for CO2 release for arene = benzene follow the order MsEn > TsEn > TfEn, and for the MsEn system the barrier followed bn < hmb, both consistent with the observed rates. The effect of methanol on transfer hydrogenation rates in aqueous solution was investigated. A study of pH dependence of the reaction in D2O gave the optimum pH* as 7.2 with a TOF of 1.58 h-1 for 2. The series of compounds reported here show an improvement in the catalytic activity by an order of magnitude compared to the ethylenediamine analogues. Do you like my blog? If you like, you can also browse other articles about this kind. Recommanded Product: Dichloro(benzene)ruthenium(II) dimer. Thanks for taking the time to read the blog about 37366-09-9

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

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Four half-sandwich ruthenium(II) complexes [(eta6-C6H6)Ru(L1-O)][PF6] (1), [(eta6-C6H6)Ru(L2-O)][PF6] (2), [(eta6-C6H6)Ru(L3-O)][PF6] (3), [(eta6-C6H6)Ru(L4-O)][PF6] (4a), and [(eta6-C6H6)Ru(L4-O)][BPh4] (4b) [L1-OH, 4-nitro-6-{[(2?-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L2-OH, 2,4-di-tert-butyl-6-{[(2?-(pyridin-2-yl)ethyl)methylamino]methyl}-phenol; L3-OH, 2,4-di-tert-butyl-6-{[2?-((pyridin-2-yl)benzylamino)methyl}-phenol; L4-OH, 2,4-di-tert-butyl-6-{[(2?-imethylaminoethyl)methylamino]methyl}-phenol (L4-OH)], supported by a systematically varied series of tridentate phenolate-based pyridylalkylamine and alkylamine ligands are reported. The molecular structures of 1-3, 4a, and 4b have been elucidated in solution using 1H NMR spectroscopy and of 1, 3, and 4b in the solid state by X-ray crystallography. Notably, due to coordination by the ligands the Ru center assumes a chiral center and in turn the central amine nitrogen also becomes chiral. The 1H NMR spectra exhibit only one set of signals, suggesting that the reaction is completely diastereoselective [1: SRu,SN/RRu,RN; 2: RRu,RN/SRu,SN; 3: SRu,RN/RRu,SN; 4b: SRu,RN/RRu,SN]. The crystal packing in 1 and 3 is stabilized by C-H…O interactions, in 4b no meaningful secondary interactions are observed. From the standpoint of generating phenoxyl radical, as investigated by cyclic voltammetry (CV), complex 1 is redox-inactive in MeCN solution. However, 2, 3, and 4a generate a one-electron oxidized phenoxyl radical coordinated species [2]2+{radical dot}, [3]2+{radical dot}, and [4a]2+{radical dot}, respectively. The radical species are characterized by CV, UV-Vis, and EPR spectroscopy. The stability of the radical species has been determined by measuring the decay constant (UV-Vis spectroscopy).

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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 reaction of [(eta6-C6H6)RuCl2]2 with the sodium salt of (+)(S)-N-(1-phenylethyl)-pyrrolecarbaldimine (HLL*) in CH2Cl2 yielded a mixture of the two diastereomers (SRu,SC)-and (RRu,SC)-[(eta6-C6H 6)Ru(LL*)Cl] (1a,b) in a ratio of 68:32. The chloride ligand in 1a,b was replaced in methanol by triphenylphosphane to give the two diastereomers (SRu,SC)-and (RRu,SC)-[eta6-C6H 6)Ru(LL*)(PPh3)]PF6 (2a,b). According to variable-temperature 1H NMR studies the formation of configurationally labile solvate intermediates has to be assumed in the reaction of the chloro complexes 1a,b with triphenylphosphane in the solvent methanol. In contrast to the diastereomers 1a,b, the ruthenium configuration in the phosphane complexes 2a,b is configurationally stable at room temperature. The diastereomers 2a,b were separated by crystallization. The crystal structures of (SRu,SC)-1a, (SRu,SC)-2a, and (RRu,SC)-2b were determined by X-ray analysis. The epimerization of 2b at 85 C in nitromethane-d3 gave a 93.5:6.5 equilibrium mixture of 2a and 2b (tau1/2 (min) = 58.2 ± 0.4). Conformational analyses showed that two main factors govern the orientation of the 1-phenylethyl group relative to the [(eta6-C6H6)Ru(LL*)X] moiety (X = Cl, PPh3): (i) the faceon orientation of the phenyl substituent with respect to the pi-bonded benzene ligand and (ii) the orientation of the hydrogen substituent toward the unidentate ligand L.

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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 of chiral mono- and bis-annelated 1,3-cyclopentadienes derived from tartaric acid, a chiral pool starting material, is described. In addition to known functionalized chiral 1,3-cyclopentadienes, new derivatives have also been structurally characterized by X-ray crystallographic and NMR spectroscopic studies. Neutral and cationic ruthenium(II) complexes, containing a mono-annelated chiral cyclopentadienyl ligand (1), have been successfully prepared. The X-ray crystal structure of [(eta5-Cp?) Ru(eta6-benzene)]-[PF6], Cp? = 1, has been determined.

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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 abundance and evolving pathogenic behavior of bacterial microorganisms give rise to antibiotic tolerance and resistance which pose a danger to global public health. New therapeutic strategies are needed to keep pace with this growing threat. We propose a novel approach for targeting bacteria by harnessing formate, a cell metabolite found only in particular bacterial species, to activate an antibacterial prodrug and selectively inhibit their growth. This strategy is premised on transfer hydrogenation reaction on a biorthogonal substrate utilizing native formate as the hydride source as a means of uncaging an antibacterial prodrug. Using coordination-directed 3-component assembly to prepare a library of 768 unique Ru?Arene Schiff-base complexes, we identified several candidates that efficiently reduced sulfonyl azide functional group in the presence of formate. This strategy paves the way for a new approach of targeted antibacterial therapy by exploiting unique bacterial metabolites.

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