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Dehydrogenation of formic acid over various Ru-arene complexes containing N-donor chelating ligands was investigated in H2O and isolated and characterized several important catalytic intermediate species to elucidate the reaction pathway for formic acid dehydrogenation. Among the studied complexes, Ru-arene complexes, namely [(eta6-C6H6)Ru(kappa2-NpyNH2-AmQ)Cl]+ (C-2), [(eta6-C10H14)Ru(kappa2-NpyNH2-AmQ)Cl]+ (C-3) and [(eta6-C6H6)Ru(kappa2-NpyNHMe-MAmQ)Cl]+ (C-4) [AmQ = 8-aminoquinoline and MAmQ = 8-(N-methylamino)quinoline] were proved to be the efficient catalysts for formic acid dehydrogenation at 90 C, even in the absence of base. With an initial TOF of 940 h?1, complex C-4 displayed the highest catalytic activity for formic acid dehydrogenation in H2O and it can be recycled up to 5 times with a TON of 2248. Effect of temperature, pH, formic acid and catalyst concentration on the reaction kinetics were also investigated in detail. Extensive mechanistic investigations using mass spectrometry and NMR evidenced the formation of a coordinatively unsaturated species [(eta6-C6H6)Ru(kappa2-NpyNH-AmQ)]+ (C-2A)/[(eta6-C6H6)Ru(kappa2-NpyNMe-MAmQ)]+ (C-4A) as the active component during the catalytic dehydrogenation of formic acid. We further characterized the dimer-form of C-2A, possibly the catalyst resting state, by single-crystal X-ray crystallography.

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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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Stable dinuclear transition metal complexes,[(I·6- C6H6)2Ru2(L1)Cl2] 2+ (1), [(I·6-p-iPrC6H 4Me)2Ru2(L1)Cl2]2+ (2), [(I·6-C6Me6)2Ru 2(L1)Cl2]2+ (3), [(I·6- C6H6)2Ru2(L2)Cl2] 2+ (4),[(I·6-p-iPrC6H 4Me)2Ru2(L2)Cl2]2+ (5), [(I·6-C6Me6)2Ru 2(L2)Cl2]2+ (6), [(I·5- C5Me5)2Rh2(L1)Cl2] 2+ (7), [(I·5-C5Me 5)2Ir2(L1)Cl2]2+ (8),[(I·5-C5Me5) 2Rh2(L2)Cl2]2+ (9), and [(I·5-C5Me5)2Rh 2(L2)Cl2]2+ (10), with the bis-bidentate ligands 1,3-bis(di-2-pyridylaminomethyl)benzene (L1) and 1,4-bis(di-2- pyridylaminomethyl)benzene (L2), which contain two chelating dipyridylamine units connected by an aromatic spacer, were synthesized. The cationic dinuclear complexes were isolated as their hexafluorophosphate salts and characterized by using a combination of NMR, IR, and UV/Vis spectroscopic methods and mass spectrometry. The solid-state structure of complex 8 as a representative was determined by X-ray structure analysis. 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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Polar phosphonic acid-derived Ru-BINAP systems were used to catalyze asymmetric hydrogenation of beta-keto esters in room temperature ionic liquids (RTILs) with complete conversions and ee values higher than those obtained from homogeneous reactions in MeOH (up to 99.3%), and were recycled by simple extraction and used for four times without the loss of activity and enantioselectivity.

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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 water soluble compounds of general formula [{(eta6-arene)Ru(HMP)Cl}], [eta6-arene = eta6-cymene (1), eta6-HMB (2), eta6-C6H6 (3); HMP = 5-hydroxy-2-(hydroxymethyl)-4-pyrone] have been prepared by the reaction of [{(eta6-arene) RuCl2}2] with HMP. The complexes 1 and 2 react with NaN3 to give in excellent yield tetra-azido complexes [{(eta6-arene)Ru(muN3)N3}2] (arene = cymene 4, HMB = 5) but similar reaction of complex 3 with NaN3 yielded di-azdo complex [{(eta6-C6H6)Ru(muN3)Cl}2] (6). Reaction of [{(eta6-arene)Ru(muN3)Cl}2] with HMP in the presence of NaOMe resulted in the formation of azido complex [{(eta6-arene)Ru(HMP)N3}]. Mono and dinuclear complexes [{(eta6-arene)Ru(HMP)(L1)}]+ and [{(eta6-arene)Ru(HMP)}2(muL2)]2+ were also prepared by the reaction of complexes 1 and 2 with the appropriate ligand, L1 or L2 in the presence of AgBF4 (L1 = PyCN, DMAP; L2 = 4,4?-bipy, pyrazine). The complexes are characterized on the basis of spectroscopic data and molecular structures of three representative compounds have been determined by single crystal X-ray diffraction study.

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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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Three new complexes, [(eta6-C6H6)RuCl(C5H4N-2-CH=N-Ar)]PF6 (Ar = phenylmethylene (1), (4-methoxyphenyl)methylene (2), and phenylhydrazone (3)), were prepared by reacting [(eta6-C6H6)Ru(mu-Cl)Cl]2 with N,N?-bidentate ligands in a 1 : 2 ratio. Full characterization of the complexes was accomplished using 1H and 13C NMR, elemental and thermal analyses, UV?vis and IR spectroscopy and single crystal X-ray structures. Single crystal structures confirmed a pseudo-octahedral three-legged, piano-stool geometry around Ru(II), with the ligand coordinated to the ruthenium(II) through two N atoms. The cytotoxicity of the mononuclear complexes was established against three human cancer cell lines and selectivity was also tested against non-cancerous human epithelial kidney (HEK 293) cells. The compounds were selective toward the tumor cells in contrast to the known anti-cancer drug 5-fluoro uracil which was not selective between the tumor cells and non-tumor cells. All the compounds showed moderate activity against MCF7 (human breast adenocarcinoma), but showed low antiproliferative activity against Caco-2 and HepG2. Also, antimicrobial activities of the complexes were tested against a panel of antimicrobial-susceptible and -resistant Gram-negative and Gram-positive bacteria. Of special interest is the anti-mycobacterial activity of all three synthesized complexes against Mycobacteriumsmegmatis, and bactericidal activity against resistant Enterococcusfaecalis and methicillin-resistant Staphylococcusaureus ATCC 43300.

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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 new potentially bidentate pyrazole-phosphinite ligands [(3,5-dimethyl-1H-pyrazol-1-yl)methyl diphenylphosphinite] (L1) and [2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyl diphenylphosphinite] (L2) were synthesised and characterised. The reaction of L1 and L2 with the dimeric complexes [Ru(eta6-arene)Cl2] 2 (arene = p-cymene, benzene) led to the formation of neutral complexes [Ru(eta6-arene)Cl2(L)] (L = L1, L2) where the pyrazole-phosphinite ligand is kappa1-P coordinated to the metal. The subsequent reaction of these complexes with NaBPh4 or NaBF4 produced the [Ru(eta6-p- cymene)Cl(L2)][BPh4] and [Ru(eta6-benzene) Cl(L2)][BF4] compounds which contain the pyrazole-phosphinite ligand kappa2-P,N bonded to ruthenium. All the complexes were fully characterised by analytical and spectroscopic methods. The structure of the complex [Ru(eta6-p-cymene)Cl(L 2)][BPh4] was also determined by a X-ray single crystal diffraction study.

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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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New series of mono and binuclear arene ruthenium complexes [{(eta6-arene)RuCl(L)}]+ and [{(eta6-arene)RuCl}2(mu-L)2] 2+ (arene=benzene, p-cymene or hexamethylbenzene), {L=pyridine-2-carbaldehyde azine (paa), p-phenylene-bis(picoline)-aldimine (pbp) and p-bi-phenylene-bis (picoline)-aldimine (bbp)} are reported. The complexes have been fully characterized and molecular structure of the representative mononuclear complex [(eta6-C6Me6) RuCl(paa)]BF4 (1), binuclear complexes [{(eta6-C10H14)RuCl}2 (mu-paa)](BF4)2 (3) and [{(eta6-C10H14) RuCl}2(mu-pbp)](BF4)2 (6) have been determined by single crystal X-ray diffraction analyses. Single crystal X-ray structure determination revealed that in the binuclear complexes the [(eta6-C10H14) RuCl]+ units are trans disposed. Further, the crystal packing in the complexes 1, 3 and 6 is stabilized by C-H?X type (X=Cl, F) inter, intramolecular hydrogen bonding and pi-pi stacking (3). To explore the ambiguous nature of the bonding between pyridine-2-carbaldehyde azine (paa) with ruthenium containing units [(eta6-arene)RuCl]+, DFT/B3LYP calculations have been performed on the complexes [(eta6-arene) RuCl(paa)]+ (arene=C6H6, I; C6Me6, II; C10H14, III).

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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 meso-pyridyl substituted dipyrromethane ligands 5-(4-pyridyl)dipyrromethane (4-dpmane) and 5-(3-pyridyl)dipyrromethane (3-dpmane) have been employed in the synthesis of a series of complexes with the general formulations [(eta6-arene)RuCl2(L)] (eta6-arene = C6H6, C10H14) and [(eta5-C5Me5)MCl2(L)] (M = Rh, Ir). The reaction products have been characterized by microanalyses and spectral studies and molecular structures of the complexes [(eta6-C10H14)RuCl2(4-dpmane)] and [(eta5-C5Me5)IrCl2(3-dpmane)] have been determined crystallographically. For comparative studies, geometrical optimization have been performed on the complex [(eta5-C5Me5)IrCl2(4-dpmane)] using exchange correlation functional B3LYP. Optimized bond length and angles are in good agreement with the structural data of the complex [(eta5-C5Me5)IrCl2(3-dpmane)]. The complexes [(eta6-C10H14)RuCl2(3-dpmane)], [(eta5-C5Me5)RhCl2(3-dpmane)] and [(eta5-C5Me5)IrCl2(3-dpmane)] have been employed as a transfer hydrogenation catalyst in the reduction of aldehydes. It was observed that the rhodium and iridium complexes mentioned above are more effective in this regard in comparison to the ruthenium complex.

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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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Three new ruthenium(II)-arene complexes, namely [(eta6-p-cymene)Ru(Me2dppz)Cl]PF6 (1), [(eta6-benzene)Ru(Me2dppz)Cl]PF6 (2) and [(eta6-p-cymene)Ru(aip)Cl]PF6 (3) (Me2dppz = 11,12-dimethyldipyrido[3,2-a:2?,3?-c]phenazine; aip = 2-(9-anthryl)-1H-imidazo[4,5-f] [1,10] phenanthroline) have been synthesized and characterized using different spectroscopic techniques including elemental analysis. The complexes were found to be well soluble and stable in DMSO. The biological activity of the three complexes was tested in three different human cancer cell lines (A549, MDA-MB-231 and HeLa) and in one human non-cancerous cell line (MRC-5). Complexes 1 and 3, carrying eta6-p-cymene as the arene ligand, were shown to be toxic in all cell lines in the low micromolar/subnanomolar range, with complex 1 being the most cytotoxic complex of the series. Flow cytometry analysis revealed that complex 1 caused concentration- and time-dependent arrest of the cell cycle in G2-M and S phases in HeLa cells. This event is followed by the accumulation of the sub-G1 DNA content after 48 h, in levels higher than cisplatin and in the absence of phosphatidylserine externalization. Fluorescent microscopy and acridine orange/ethidium bromide staining revealed that complex 1 induced both apoptotic and necrotic cell morphology characteristics. Drug-accumulation and DNA-binding studies performed by inductively coupled plasma mass spectrometry in HeLa cells showed that the total ruthenium uptake increased in a time- and concentration-dependent manner, and that complex 1 accumulated more efficiently than cisplatin at equimolar concentrations. The introduction of a Me2dppz ligand into the ruthenium(II)-p-cymene scaffold was found to allow the discovery of a strongly cytotoxic complex with significantly higher cellular uptake and DNA-binding properties than cisplatin.

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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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Redox potentials of photosensitive cyclometalated RuII derivatives of 2-phenylpyridine or 2-(4-tolyl)pyridine are controllably decreased by up to 0.8 V within several minutes. This is achieved by irradiation of the ruthena(II)cycles cis-[Ru(o-X-2-py)(LL)(MeCN)2]PF6 (2, X = C6H4 (a) or 4-MeC6H3 (b), LL = 1,10-phenanthroline or 2,2?-bipyridine). The cis geometry of the MeCN ligands has been confirmed by the X-ray structural studies. The sigma-bound sp2 carbon of the metalated ring is trans to LL nitrogen. Complexes 2 are made from [Ru(o-X-2-py)(MeCN)4]PF6 (1) and LL. This “trivial” ligand substitution is unusual because 1a reacts readily with phen in MeCN as solvent to give cis-[Ru(o-C6H 4-2-py)(phen)(MeCN)2]PF6 (2c) in a 83% yield, but bpy does not afford the bpy-containing 2 under the same conditions. cis-[Ru(o-C6H4-2-py)(bpy)(MeCN)2]PF 6 (2e) has been prepared in CH2Cl2 (74%). Studies of complexes 2c,e by cyclic voltammetry in MeOH in the dark reveal RuII/III quasy-reversible redox features at 573 and 578 mV (vs Ag/AgCl), respectively. A minute irradiation 2c and 2e converts them into new species with redox potentials of -230 and 270 mV, respectively. An exceptional potential drop for 2c is accounted for in terms of a photosubstitution of both MeCN ligands by methanol. ESR, 1H NMR, and UV-vis data indicate that the primary product of photolysis of 2c is an octahedral monomeric low-spin (S = 1/2) RuIII species, presumably cis-[RuIII(o-C 6H4-2-py)(phen)(MeOH)2]2+. The primary photoproduct of bpy complex 2e is cis-[RuII(o-C 6H4-2-py)(bpy)(MeCN)-(MeOH)]+, and this accounts for a lower decrease in the redox potential. Irradiation of 2c in the presence of added chloride affords [(phen)(o-C6H4-2-py) ClRuIIIORuIVCl(o-C6H4-2-py)(phen)] PF6, a first mu-oxo-bridged mixed valent dimer with a cyclometalated unit. The structure of the dimer has been established by X-ray crystallography.

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