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We have developed a new strategy that uses the Kroehnke synthesis for the preparation of various substituted phenylpyridines in excellent yields (up to 88%). Starting with the appropriate commercially available acetophenone, a variety of phenylpyridines substituted by either electron-donating (i.e. methyl, methoxy) or -withdrawing groups (i.e. bromide, nitro) on the phenyl ring are obtained in a two-step synthesis. The corresponding functionalized cyclometalated ruthenium complexes can be prepared with unusually high yields by using methanol as reaction solvent. The electrochemical data of the complexes demonstrate the strong sigma-donating character of the anionic phenylpyridine ligand. X-ray analyses of four complexes show a shortening of the Ru-C bond associated with the elongation of only one of the five Ru-N bonds (trans effect). Wiley-VCH Verlag GmbH & Co, KGaA, 2006.

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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 new series of ruthenium polypyridyl complexes with a hydroxypyridine ligand were prepared, and their properties were investigated spectroscopically and electrochemically. Particular focus is paid to the effects of protonation-deprotonation and ethylation of the hydroxypyridine ligand, which affects the NMR, electronic spectroscopy, and electrochemistry of the complex. The changes to the UV-vis spectrum were used to determine a pka of 10.5 for the hydroxypyridine nitrogen. In the NMR, protonation of the hydroxypyridine ligand of the complex causes changes in the chemical shifts of the protons on both the hydroxypyridine and bipyridine rings, indicating some degree of electronic communication between these ligands. In addition, it is found that deprotonation of the hydroxypyridine ligand strongly affects the redox potential of the ruthenium metal center, shifting it more negative by 0.4 V. While the electrochemistry of the protonated complex contains irreversible electrochemical events, both deprotonation and subsequent ethylation of the hydroxypyridine ligand result in reversible electrochemistry for all events within the solvent window. For the ethylated complex, we search for a ligand to ligand charge transfer band, corresponding to electron transfer between bipyridine ligands in the mixed valence state. Despite the potential for electronic coupling between ligands through the metal center, we were unable to find any spectroscopic evidence of such electronic coupling. The Royal Society of Chemistry 2013.

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

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

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Phenazinic ligands and Ru(ii)-based complexes were synthesized from natural products lapachol and lawsone and evaluated against T. cruzi, the etiological agent of Chagas disease. These new ruthenium compounds could provide promising trypanocidal drugs. Besides synthesis and trypanocidal activity, this paper reports photophysical features and computational details of the compounds. The fluorescent trypanocidal substances are promising derivatives for further studies aiming to find molecules active against parasites associated with neglected diseases.

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

Can You Really Do Chemisty Experiments 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, SDS of cas: 15746-57-3

Two new aldehyde-decorated tpy and bpy-containing ruthenium(II) complexes, [Ru(1)(bpy)2][PF6]2 and [Ru(1)(tpy)Cl][PF6] in which 1 is 5,5?-bis(4-formylphenyl)-2,2?-bipyridine, have been prepared and fully characterized. The packing in both solid state structures involves extensive Oaldehyde···HCpyridine contacts, but pi-stacking interactions are important only between [Ru(1)(tpy)Cl]+ cations.

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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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Photoinduced intramolecular electron transfers within ligand-bridged Ru(II) and Co(III) compounds of <(bpy)2Ru(L)Co(bpy)2>(5+) (a, b, and c) were examined in butyronitrile by means of laser photolysis kinetic spectroscopy, where L is a bridging tetradentate ligand, 2,6-bis(2-pyridyl)benzodiimidazole for a, 2,2′-bis(2-pyridyl)bibenzimidazole for b, and 1,5-bis<2-(2-pyridyl)benzimidazoyl>pentane for c.The temperature dependence of the rates of electron transfer and intersystem crossing is analyzed by taking the temperature dependence of the Gibbs energy change and reorganization energy into account.A transient difference absorption band at 420 nm observed after the picosecond laser excitation of a and b is not ascribed to the formation of excited Ru(II) moiety but to the reaction product (2Co(II)) of the Co(III) moiety, which decayed to form a long-lived species of 4Co(II) within 1 ns below 270 K.The inner-sphere reorganization of the intersystem crossing of 2Co(II) -> 4Co(II) is estimated to be 0.6 eV from the temperature dependence of the transition rate.The electron transfer from the excited MLCT state of the Ru(II) moiety to Co(III) for c occured within 1 ns at 300 K.The inner-sphere reorganization energy (0.6 eV) of the electron transfer was determined from the temperature-dependent electron transfer rate observed.The back electron transfer from 4Co(II) to 2Ru(III) was much slower than the initial electron transfer.It is not the small electronic coupling between 4Co(II) and 2Ru(III) but the negative entropy change (-1.3 meV/K) of Co(II) oxidation that is responsible for the small frequency factor of the electron transfer process.The inner-sphere organization energy of the back electron transfer was determined (1.1-1.3 eV) from the temperature-dependent rate.

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

Final Thoughts on Chemistry for Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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Ruthenafuran and osmafuran monocationic complexes [Ru([14]aneS4)(C?O)]+ or [M(bpy)2(C?O)]+ (C?O = anionic bidentate chelate [C(OR)CHC(Ph)-O]-; [14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane; M = Ru, Os; bpy = 2,2?-bipyridine) have been prepared from reactions between phenyl-ynone HC-C(CO)Ph and [Ru([14]aneS4)Cl2] or [M(bpy)2Cl2] in alcoholic solvents ROH. The formation of metal-vinylidene intermediate, followed by nucleophilic attack by RO-, and carbonyl group coordination to the metal center are believed to be the key steps in the formation of these metallafurans. The nature of the anionic C?O ligand was investigated by electrochemical, spectroscopic, and theoretical means.

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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 new 2-pyridyl-1,2,3-triazole (pytri) ligand, TPA-pytri, substituted with a triphenylamine (TPA) donor group on the 5 position of the pyridyl unit was synthesized and characterized. Dichloroplatinum(II), bis(phenylacetylide)platinum(II), bromotricarbonylrhenium(I), and bis(bipyridyl)ruthenium(II) complexes of this ligand were synthesized and compared to complexes of pytri ligands without the TPA substituent. The complexes of unsubstituted pytri ligands show metal-to-ligand charge-transfer (MLCT) absorption bands involving the pytri ligand in the near-UV region. These transitions are complemented by intraligand charge-transfer (ILCT) bands in the TPA-pytri complexes, resulting in greatly improved visible absorption (lambdamax = 421 nm and ? = 19800 M-1 cm-1 for [Pt(TPA-pytri)Cl2]). The resonance Raman enhancement patterns allow for assignment of these absorption bands. The [Re(TPA-pytri)(CO)3Br] and [Pt(TPA-pytri)(CCPh)2] complexes were examined with time-resolved infrared spectroscopy. Shifts in the C?C and C?O stretching bands revealed that the complexes form states with increased electron density about their metal centers. [Pt(TPA-pytri)Cl2] is unusual in that it is emissive despite the presence of deactivating d-d states, which prevents emission from the unsubstituted pytri complex.

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

Discovery of Cis-Dichlorobis(2,2′-bipyridine)ruthenium(II)

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A diruthenium(II) complex, [{Ru(bpy)2}2(mu-Haet) 2]4+ ([1]4+, Haet = -SCH 2CH2NH3+), which consists of two cis-[Ru(bpy)2]2+ units bridged by two thiolato groups, was newly prepared and separated into meso and racemic isomers. The spectroscopic and electrochemical properties of [1]4+, together with the crystal structure of its meso isomer, are reported. 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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A novel microwave-assisted synthetic method has been used to synthesise a series of mixed ligand ruthenium(II) compounds containing diimine as well as bidentate thiosemicarbazone ligands. The compounds contain the diimine 1,10-phenanthroline (phen) or 2,2?-bipyridine (bpy) and the thiosemicarbazone is derived from 9-anthraldehyde. Based on elemental analyses and spectroscopic data, the compounds are best formulated as [(phen) 2Ru(thiosemicarbazone)](PF6)2 and [(phen) 2Ru(thiosemicarbazone)](PF6)2 where thiosemicarbazone = 9-anthraldehydethiosemicarbazone, 9-anthraldehyde-N(4)- methylthiosemicarbazone, and 9-anthraldehyde-N(4)-ethylthiosemicarbazone. Fluorescence competition studies with ethidium bromide, along with viscometric measurements suggests that the complexes bind calf thymus DNA (CTDNA) relatively strongly via an intercalative mode possibly involving the aromatic rings of the diimine ligands. The complexes show good cytotoxic profiles against MCF-7 and MDA-MB-231 (breast adenocarcinoma) as well as HCT 116 and HT-29 (colorectal carcinoma) cell lines. The Royal Society of Chemistry 2009.

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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 feasibility of devising a solid support mediated approach to multimodal Ru(II)-peptide nucleic acid (PNA) oligomers is explored. Three Ru(II)-PNA-like monomers, [Ru(bpy)2(Cpp-L-PNA-OH)]2+ (M1), [Ru(phen) 2(Cpp-L-PNA-OH)]2+ (M2), and [Ru(dppz)2(Cpp-L- PNA-OH)]2+ (M3) (bpy = 2,2?-bipyridine, phen = 1,10-phenanthroline, dppz = dipyrido[3,2-a:2?,3?-c]phenazine, Cpp-L-PNA-OH = [2-(N-9-fluorenylmethoxycarbonyl)aminoethyl]-N-[6-(2-(pyridin- 2yl)pyrimidine-4-carboxamido)hexanoyl]-glycine), have been synthesized as building blocks for Ru(II)-PNA oligomers and characterized by IR and 1H NMR spectroscopy, mass spectrometry, electrochemistry and elemental analysis. As a proof of principle, M1 was incorporated on the solid phase within the PNA sequences H-g-c-a-a-t-a-a-a-a-Lys-NH2 (PNA1) and H-P-K-K-K-R-K-V-g-c-a-a-t-a-a-a-a-lys-NH2 (PNA4) to give PNA2 (H-g-c-a-a-t-a-a-a-a-M1-lys-NH2) and PNA3 (H-P-K-K-K-R-K-V-g-c-a-a-t- a-a-a-a-M1-lys-NH2), respectively. The two Ru(II)-PNA oligomers, PNA2 and PNA3, displayed a metal to ligand charge transfer (MLCT) transition band centered around 445 nm and an emission maximum at about 680 nm following 450 nm excitation in aqueous solutions (10 mM PBS, pH 7.4). The absorption and emission response of the duplexes formed with the cDNA strand (DNA: 5?-T-T-T-T-T- T-T-A-T-T-G-C-T-T-T-3?) showed no major variations, suggesting that the electronic properties of the Ru(II) complexes are largely unaffected by hybridization. The thermal stability of the PNA?DNA duplexes, as evaluated from UV melting experiments, is enhanced compared to the corresponding nonmetalated duplexes. The melting temperature (Tm) was almost 8 C higher for PNA2?DNA duplex, and 4 C for PNA3?DNA duplex, with the stabilization attributed to the electrostatic interaction between the cationic residues (Ru(II) unit and positively charged lysine/arginine) and the polyanionic DNA backbone. In presence of tripropylamine (TPA) as co-reactant, PNA2, PNA3, PNA2?DNA and PNA3?DNA displayed strong electrochemiluminescence (ECL) signals even at submicromolar concentrations. Importantly, the combination of spectrochemical, thermal and ECL properties possessed by the Ru(II)-PNA sequences offer an elegant approach for the design of highly sensitive multimodal biosensing tools.

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