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The mononuclear cations of the general formula [(eta6-arene)RuCl(dpqMe2)]+ (dpqMe2 = 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline; arene = C6H6, 1; C6H5Me, 2; p-PriC6H4Me, 3; C6Me6, 4) as well as the dinuclear dications [(eta6-arene)2Ru2Cl2(mu-dpqMe2)]2+ (arene = C6H6, 5; C6H5Me, 6; p-PriC6H4Me, 7; C6Me6, 8) have been synthesised from 6,7-dimethyl-2,3-di(pyridine-2-yl)quinoxaline (dpqMe2) and the corresponding chloro complexes [(eta6-C6H6)Ru(mu-Cl)Cl]2, [(eta6-C6H5Me)Ru(mu-Cl)Cl]2, [(eta6-p-PriC6H4Me)Ru(mu-Cl)Cl]2 and [(eta6-C6Me6)Ru(mu-Cl)Cl]2, respectively. The X-ray crystal structure analyses of [1][PF6], [3][PF6] and [6][PF6]2 reveal a typical piano-stool geometry around the metal centre; in the dinuclear complexes the two chloro ligands, with respect to each other, are found to be trans oriented.

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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 [{RuCl2(eta6-o-MeC6H4CO 2Me)}2], (o-MeC6H4CO2Me = methyl o-toluate), from RuCl3·3H2O and methyl 1,4-dihydro-o-toluate is reported. This is the first example of an arene-ruthenium complex having planar chirality with respect to the face of the co-ordinated arene. Its reactions with tertiary phosphines and primary amines have been examined. Using optically active amines, the complexes [RuCl2(eta6-o-MeC6H4CO 2Me) L?] [L? = (-)(S)-1-phenylethylamine or (+)-dehydroabietylamine], and [RuCl(eta6-o-MeC6H4CO 2Me)(N-N)]PF6 [N-N = (-)(R,R)-1,2-diphenyl-1,2-diaminoethane], have been obtained as diastereomeric mixtures. The diastereomers of [RuCl2(eta6-o-MeC6H4CO 2Me){(-)(S)-MeCH(Ph)NH2}] have been partially separated by fractional crystallisation, the less soluble one being obtained with > 90% enrichment. Their circular dichroism spectra have been compared with those of complexes containing achiral arene-ruthenium moieties.

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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 [{Ru(eta6-C6H6)Cl(mu-Cl)}2] with Py3COH in ethanol results in the formation of the cation [Ru(eta6-C6H6)(N,N?,O,-(C 5H4N)3CO)]+ which is isolated as its hexafluorphosphate salt 1. The cation acts as a ligand towards other transition metal ions. With Ag+ the hetero-trinuclear complex [{Ru(eta6-C6H6)((C5H 4N)3CO)}2Ag][PF6]3 2 is formed, while reaction with [Pd(PhCN)2Cl2] gives the bimetallic [Ru(eta6-C6H6)((C5H 4N)3CO)PdCl2][PF6] 3. Both compounds were fully characterised by spectroscopic methods and the trinuclear complex was additionally characterised by X-ray diffraction. Elsevier Science Ltd.

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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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Ruthenium complexes [(eta5-C5H5) Ru(PPh3)(kappa2-paa)]PF6 (paa = pyridine-2-carbaldehyde azine) and [(eta5-C5H 5)Ru(kappa1-dppm)-(kappa2-paa)]BF 4 [dppm = bis(diphenylphosphanyl)methane] have been employed as a synthon in the synthesis of homo/hetero bi-/trimetallic complexes. It is the uncoordinated N,N-donor site on paa in complex [(eta5-C 5H5)Ru(PPh3)-(kappa2-paa)]PF 6, and N,N-donor site on paa and pendant phosphorus in [(eta5-C5H5)Ru(kappa1-dppm) (kappa2-paa)]BF4 that allows for their incorporation into bi-/trimetallic systems. The resulting complexes have been characterized by analytical, spectral and electrochemical studies. Molecular structures of homobimetallic complex [(PPh3)(theta5-C 5H5)Ru(mu-paa)Ru(theta6-C 10H14)Cl](PF6)2 and hetero-bimetallic complex [(PPh3)(theta5-C 5H5)-Ru(mu-paa)Rh(theta5-C 5Me5)Cl](PF6)2 have been authenticated crystallographically. Complexes exhibit absorptions throughout the visible region and complicated electrochemical behaviour. Metal-based Ru II/RuIII oxidations in the bimetallic complexes do not vary as in the trimetallic complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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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 Patent,once mentioned of 37366-09-9, Quality Control of: Dichloro(benzene)ruthenium(II) dimer

The present invention relates to uses or methods for treating proliferative diseases, in particular cancer, implementing ruthenium compounds, as well as to composition containing same.

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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 ligand [2-chloro-3-(3-(2-pyridyl)pyrazolyl)quinoxaline] (L) have been prepared from 2,3-dichloroquinoxaline and 3-(2-pyridyl)-1H-pyrazole. The reaction of N,N?-bidentate chelating ligand (L) and the corresponding metal precursors [(arene)Ru(mu-Cl)Cl]2 {arene = p-cymene, benzene, hexamethylbenzene (HMB)}, [Cp?M(mu-Cl)Cl]2 {Cp? = pentamethylcyclopentadiene; M = Rh, Ir}, [CpRuCl(PPh3)2] {Cp = cyclopentadiene; PPh3 = triphenylphosphine} and [Re(CO)5Br] leads to the formation of mononuclear metal complexes having the general formula [(arene)Ru(L)Cl]+ where, arene = p-cymene (1), C6H6 (2), C6Me6 (3), [Cp?M(L)Cl]+ where, M = Rh (4), Ir (5), [CpRu(L)PPh3]+ (6) and [Re(L)(CO)3Br] (7). All these platinum group metal complexes were synthesized and isolated with PF6 counter anions except complex (6) whereas the complex (7) was isolated as a neutral complex. All these metal complexes were fully characterized by FT-IR, 1H NMR, UV-Vis and mass spectroscopic and analytical techniques. Moreover, the complexes (1-7) were determined by the single-crystal X-ray diffraction analysis. Single crystal X-ray data confirms that the coordination occurs to the N-atoms of the pyridyl and pyrazolyl moieties of the ligand. Agar well diffusion method reveals that complexes (1, 2, 4 and 5) are having good antibacterial activity against the three different bacteria, pathogenic test organisms Staphylococcus aureus subsp. aureus, Staphylococcus epidermidis and Escherichia coli. The electronic transitions and absorption band of the complexes calculated by using time-dependent DFT method are in good agreement with the experimental results.

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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 quite general approach for the preparation of eta5- and eta6-cyclichydrocarbon platinum group metal complexes is reported. The dinuclear arene ruthenium complexes [(eta6-arene)Ru(mu-Cl)Cl] 2 (arene = C6H6, C10H14 and C6Me6) and eta5- pentamethylcyclopentadienyl rhodium and iridium complexes [(eta5- C5Me5)M(mu-Cl)Cl]2 (M = Rh and Ir) reacts with two equivalents of the ligands 2-chloro-3-(pyrazolyl)quinoxaline (L 1) and di-(2-pyridyl)amine (L2) in presence of NH 4PF6 to afford the corresponding mononuclear complexes of the type [(eta6-arene)Ru(L1)Cl]PF6 {arene = C6H6 (1), C10H14 (2) and C 6Me6 (3)}, [(eta6-arene)Ru(L 2)Cl]PF6 {arene = C6H6 (4), C 10H14 (5) and C6Me6 (6)}, and [(eta5-C5Me5)M(L1)Cl]PF 6 {M = Rh (7), Ir (8)} and [(eta5-C5Me 5)M(L2)Cl]PF6 {M = Rh (9), Ir (10)}. However the mononuclear eta5-cyclopentadienyl analogues such as [(eta5-C5H5)Ru(PPh3) 2Cl], [(eta5-C5H5)Os(PPh 3)2Br], [(eta5-C5Me 5)Ru(PPh3)2Cl] and [(eta5-C 9H7)Ru(PPh3)2Cl] complexes react in presence of one equivalent of ligands 2-chloro-3-(pyrazolyl)quinoxaline (L 1) and di-(2-pyridyl)amine (L2) and one equivalent of NH4PF6 in methanol yielded mononuclear complexes [(eta5-C5H5)Ru(PPh3)(L 1)]PF6 (11), [(eta5-C5H 5)Os(PPh3)(L1)]PF6 (12), [(eta5-C5Me5)Ru(PPh3)(L 1)]PF6 (13) and [(eta5-C9H 7)Ru(PPh3)(L1)]PF6 (14) and [(eta5-C5H5)Ru(PPh3)(L 2)]PF6 (15), [(eta5-C5H 5)Os(PPh3)(L2)]PF6 (16), [(eta5-C5Me5)Ru(PPh3)(L 2)]PF6 (17) and [(eta5-C9H 7)Ru(PPh3)(L2)]PF6 (18) respectively. These compounds have been systematically characterized by IR, NMR and mass spectrometry. The molecular structures of 2, 4 and 15 have been established by single crystal X-ray diffraction study and some of the representative complexes have also been studied by UV-visible spectroscopy. The crystal packing diagram of complex 4 reveals that the cation [(eta6-C6H6)Ru(L2)Cl]+ is engaged in non-covalent interaction. This compound gives rise to a 1D helical architecture along the ‘a’ axis via intermolecular NH?Cl hydrogen bonds.

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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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Six Ru-eta6-C6H6-diphosphine complexes, [RuCl(eta6-C6H6)(BISBI)]Cl (1) (BISBI = 2,2?-bis(diphenylphosphinomethyl)-1,1?-biphenyl), [RuCl(eta6-C6H6)(BDPX)]Cl (2) (BDPX = 1,2-bis(diphenylphosphinomethyl)benzene), Ru2Cl4(eta6-C6H6)2(mu2-BDNA) (3) (BDNA = 1,8-bis(diphenylphosphinomethyl)naphthalene), [RuCl(eta6-C6H6)(BISBI)]BF4 (4), [RuCl(eta6-C6H6)(BDPX)]BF4 (5) and [(eta6-C6H6)2Ru2Cl2(mu2-Cl)(mu2-BDNA)]BF4 (6) were prepared and used as catalysts in hydrogenation of benzene. Their catalytic activities were obviously relative with the compositions or structures of these complexes. The hydrogenations of benzene catalyzed by complexes 1, 2 and 3 were homogeneous in the conditions of reaction temperature of 100 C and hydrogen pressure of 50 kg/cm2, complexes 4, 5 and 6 were simultaneously homogeneous and heterogeneous in the same reaction conditions. Among all complexes, 4, 5 and 6 were of higher catalytic activities than 1, 2 and 3. The dinuclear complex 6 in which one chlorine anion was substituted by one tetrafluoroborate gave the highest activity. The higher activities of complex 4, 5 and 6 were owing to the easy generation of catalytic active species and the formations of Ru(0) particles which were of the highly catalytic activity. As novel complexes, the compositions and structures of 1, 2, 4 and 5 were characterized by NMR spectra. The structures of 4 and 5 were further determined by elemental analysis and single crystal X-ray diffraction.

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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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Cyclometalated derivatives of ring-substituted N,N-dimethylbenzylamines with controlled redox potentials as potent mediators of bioelectrochemical electron transport are reported. The cycloruthenation of R1R 2R3C6H2CH2NMe 2 (R1, R2, R3 = H, Me, tBuO, MeO, NMe2, F, CF3, CN, NO2) by [(eta6-C6H6)RuCl(mu-Cl)]2 in the presence of NaOH/KPF6 in acetonitrile or pivalonitrile affords cyclometalated complexes [(eta6-C6H6) Ru(C6HR1R2R3-o-CH 2NMe2)(RCN)]PF6 [R = Me (1) and R = CMe 3 (2)] in good yields. Reactions of complexes 1 and 2 with 2,2?-bipyridine (bpy) in acetonitrile or pivalonitrile result in dissociation of eta6-bound benzene and the formation of [Ru(C 6HR1R2R3-o-CH2NMe 2)(bpy)(RCN)2]PF6 [R = Me (3) and R = CMe 3 (4)]. All new compounds have been fully characterized by mass spectrometry, 1H/13C NMR, and IR spectroscopy. An X-ray crystal structural investigation of complex 1 (R1/R 2/R3 = H/H/H) and two complexes of type 3 (R 1/R2/R3 = MeO/H/H, MeO/MeO/H) has been performed. Acetonitrile ligands of 3 are mutually cis and the sigma-bound carbon is trans to one of the bpy nitrogens. Measured by the cyclic voltammetry in MeOH as solvent, the redox potentials of complexes 3 for the Ru II/III feature cover the range 320-720 mV (versus Ag/AgCl) and correlate linearly with the Hammett (sigmap++sigmam) constants. Complexes 3 mediate efficiently the electron transport between the active site of PQQ-dependent glucose dehydrogenase (PQQ = pyrroloquinoline quinone) and a glassy carbon electrode. Determined by cyclic voltammetry the second order rate constant for the oxidation of the reduced (by d-glucose) enzyme active site by RuIII derivative of 3 (R1/R2/R3 = H) (generated electrochemically) is as high as 4.8 × 107 M -1 s-1 at 25C and pH 7.

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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 strategy for targeting protein kinases with large ATP-binding sites by using bulky and rigid octahedral ruthenium complexes as structural scaffolds is presented. A highly potent and selective GSK3 and Pim1 half-sandwich complex NP309 was successfully converted into a PAK1 inhibitor by making use of the large octahedral compounds Lambda-FL172 and Lambda-FL411 in which the cyclopentadienyl moiety of NP309 is replaced by a chloride and sterically demanding diimine ligands. A 1.65 A cocrystal structure of PAK1 with Lambda-FL172 reveals how the large coordination sphere of the ruthenium complex matches the size of the active site and serves as a yardstick to discriminate between otherwise closely related binding sites. Copyright

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