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Journal articles on the topic 'Chemistry - complex di ruthenium'

Author: Grafiati

Published: 4 June 2021

Last updated: 3 February 2022

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1

BATALINI, C., and W. F. DE GIOVANI. "SYNTHESIS AND CHARACTERIZATION OF A NEW RUTHENIUM (II) DIARSINIC AQUACOMPLEX." Periódico Tchê Química 16, no. 32 (August 20, 2019): 130–38. http://dx.doi.org/10.52571/ptq.v16.n32.2019.148_periodico32_pgs_130_138.pdf.

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Ruthenium complexes are used as catalysts, energy converters, some have biological activity, among other applications. The ruthenium chemistry reserves remarkable stability when complexed with organic ligands, mainly bipyridine and tripyridine. Ruthenium polypyridine aquacomplexes have acted as excellent electrocatalysts in the conversion of organic substances, since they offer interesting patterns of binding with ruthenium. The preparation of ruthenium aquacomplexes combining tripyridine and bidentate arsine ligands is not officially described. Good advantages have been found when using ligands containing mixed mono, di or tripyridines with bidentate ligands in their coordination sphere, such as the verified stability of these complexes, without loss of ligands during the process and the possibility of better stereochemical control during the synthesis of these complexes. This work stands out the synthesis, in three stages, of a new ruthenium tripyridine complex containing a bidentate arsine: [Ru(L)(totpy)(OH2)](ClO4)2 (L=Ph2AsCH2CH2AsPh2); (totpy=4'-(4-tolyl)-2,2':6',2''-terpyridine). Each step of the synthetic route showed a significant reaction yield and the voltammetric, spectroscopic and microanalytical characterization results point positively to the proposed chemical structure of the complex.

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2

Unjaroen, Duenpen, Johann B. Kasper, and W. R. Browne. "Reversible photochromic switching in a Ru(ii) polypyridyl complex." Dalton Trans. 43, no. 45 (2014): 16974–76. http://dx.doi.org/10.1039/c4dt02430c.

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Fully reversible photoswitching of the coordination mode of the ligand MeN₄Py (1,1-di(pyridin-2-yl)-N,N′-bis(pyridin-2-yl-methyl)-ethan-1-amine) in its ruthenium(ii) complex with visible light is reported.

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3

Shimizu, Eiza, and Derrick Ethelbhert Yu. "Synthesis of Highly Soluble Axially-Ligated Ruthenium(III) Phthalocyanine Salt: Potassium Dithiocyanato(phthalocyaninato)ruthenium(III)." Oriental Journal of Chemistry 34, no. 6 (November 10, 2018): 3157–60. http://dx.doi.org/10.13005/ojc/340664.

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Partially-oxidized di-axially ligated Ruthenium(III) phthalocyanine crystalline salts are deemed to be highly conducting molecular solids with giant negative magnetoresistance. Solubility as a prerequisite for crystallization has always been a challenge especially in Ruthenium complexes. This paper presents the synthesis of highly soluble potassium dithiocyanato(phthalocyaninato(-2))ruthenium(III) salt from the poorly soluble dibromo(phthalocyaninato(-1))ruthenium(III) radical complex. The synthesis involves the reduction of the Phthalocyanine ligand and substitution of axial ligands utilizing potassium thiocyanide to afford the product.

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4

Mishra, Anurag, Sambandam Ravikumar, Young Ho Song, Nadarajan Saravanan Prabhu, Hyunuk Kim, Soon Ho Hong, Seyeon Cheon, Jaegeun Noh, and Ki-Whan Chi. "A new arene–Ru based supramolecular coordination complex for efficient binding and selective sensing of green fluorescent protein." Dalton Trans. 43, no. 16 (2014): 6032–40. http://dx.doi.org/10.1039/c3dt53186d.

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5

Weber, Immo, Frank W. Heinemann, Walter Bauer, and Ulrich Zenneck. "Configurational Flexibility of Epimeric β-Aminothioether-chelated Ruthenium(II) η6-Arene Complex Salts." Zeitschrift für Naturforschung B 64, no. 1 (January 1, 2009): 123–40. http://dx.doi.org/10.1515/znb-2009-0117.

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Five chiral β -aminothioethers were obtained via different routes orientated on literature protocols. Three of these β -aminothioethers were reacted with two di-μ-chloro-bis{chloro[η6-arene]- ruthenium(II)} derivatives, resulting in the title complex salts. The complex cations exhibit three stereocenters, viz. ruthenium and sulfur atoms and the chiral benzylic carbon atom of the chelate ligand backbone. Both, ruthenium and sulfur stereocenters epimerize into a mixture of four NMR distinguishable diastereomers in equilibrium, but the designed chiral benzylic carbon atom is stable under all conditions applied so far. The relative diastereomer concentrations in solution depend mainly on the spatial requirements of the η6-arene ligand rather than on the thioether moiety. Diastereomer ratios and the absolute configurations in solution were studied by NMR and CD spectroscopy. The spectroscopic results fit to the absolute X-ray crystal structure parameters determined for the diastereomers present in the crystalline state.

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6

Nakai, Akito, Takayuki Tanaka, and Atsuhiro Osuka. "Oxidation-Induced Detachment of Ruthenoarene Units and Oxygen Insertion in Bis-Pd(II) Hexaphyrin π-Ruthenium Complexes." Molecules 25, no. 12 (June 15, 2020): 2753. http://dx.doi.org/10.3390/molecules25122753.

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Two types of new bis-Pd(II) hexaphyrin π-ruthenium complexes are reported. A double-decker bis-Pd(II) hexaphyrin π-ruthenium complex 4 was obtained by oxidation-induced detachment of a ruthenoarene unit from the triple-decker complex 3 and oxygen-inserted triple-decker bis-Pd(II) hexaphyrin π-ruthenium complex 6 was obtained upon treatment of bis-Pd(II) [26]hexaphyrin 5 with [RuCl2(p-cymene)]2 under aerobic conditions. Although π-metal complexation of porphyrinoids often results in decreased global aromaticity due to the enhancement of local 6π aromatic segments, distinct aromatic characters were indicated for 4 and 6 by 1H-NMR spectral and theoretical calculations. These results are accounted for in terms of possible resonance contributors of hexaphyrin di- and tetraanion ligands. Thus, π-metal coordination has been shown to be effective for modulation of the overall aromaticity.

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7

Lu, Zhongkai, Yan Gao, Hu Chen, Zhao Liu, and Licheng Sun. "Water oxidation catalyzed by a charge-neutral mononuclear ruthenium(iii) complex." Dalton Transactions 46, no. 4 (2017): 1304–10. http://dx.doi.org/10.1039/c6dt04160d.

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8

Rota Martir, Diego, Mattia Averardi, Daniel Escudero, Denis Jacquemin, and Eli Zysman-Colman. "Photoinduced electron transfer in supramolecular ruthenium–porphyrin assemblies." Dalton Transactions 46, no. 7 (2017): 2255–62. http://dx.doi.org/10.1039/c6dt04414j.

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We present dynamic supramolecular systems composed of a Ru(ii) complex of the form of [Ru(dtBubpy)₂(qpy)][PF₆]₂ (where dtBubpy is 4,4′-di-tert-butyl-2,2′-dipyridyl and qpy is 4,4′:2′,2′′:4′′,4′′′-quaterpyridine) and zinc tetraphenylporphyrins (ZnTPP), through non-covalent interactions between the distal pyridines of the qpy and the zinc of ZnTPP.

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9

Glodjovic, Verica, and Srecko Trifunovic. "Stereospecific ligands and their complexes: Synthesis and characterization of the s-cis-K[Ru(S,S-eddp)Cl2]·3H2O." Journal of the Serbian Chemical Society 73, no. 5 (2008): 541–45. http://dx.doi.org/10.2298/jsc0805541g.

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In the reaction of ruthenium(III) chloride and an edda-like ligand ethylenediamine-N,N'-di-S,S-2-propionic acid (S,S-eddp) in aqueous solution led to the formation of only one of the three possible geometrical isomers potassium- s-cis-dichlorido-(ethylenediamine-N,N'-di-S,S-2-propionato)-ruthenate(III)- -trihydrate, s-cis-K[Ru(S,S-eddp)Cl2]?3H2O. The assumed geometry of the complex was based on its electronic absorption and infrared spectra.

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10

Li, Xianghong, Kun Hou, Xinfang Duan, Fuyou Li, and Chunhui Huang. "Ruthenium(II) complex based on 4,4′-di(p-methylphenyl)-2,2′-bipyridine: Synthesis and photoelectrochemical properties." Inorganic Chemistry Communications 9, no. 4 (April 2006): 394–96. http://dx.doi.org/10.1016/j.inoche.2006.01.012.

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11

Schramm, Frank, Dirk Walther, Helmar Görls, Christian Käpplinger, and Rainer Beckert. "Trifluoromethylaryl-Substituted Quinoxalines: Unusual Ruthenium- Amidininate Complexes and their Suitability for Anellation Reactions." Zeitschrift für Naturforschung B 60, no. 8 (August 1, 2005): 843–52. http://dx.doi.org/10.1515/znb-2005-0805.

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The reaction of the 2,3-dianilino-quinoxaline 1 with an equivalent of triethyl orthoformiate results in a cyclic aminalester 2. An excess of triethyl orthoformate results in the carbene dimer 4. With the help of boron trifluoride, 2 can be transformed into the imidazolium salt 3. Reaction of 1 with KOtC4H9 leads to a quinoxaline derivative 5 under anellation of a benzene ring whereas the related pyrazino-quinoxaline 6 (formed from tetraaminobenzene tetrahydrochloride and bis-(3- trifluoromethylphenyl) oxalimidoyl chloride) does not react under similar conditions. However, 6 can be activated towards anellation by employing the complex fragment [(tbbpy)2Ru]2+, tbbpy: bis(4,4’-di-tert-butyl-2,2’-bipyridine). This generates an unusual ruthenium complex 9 which could be characterised by X-ray diffraction. Complex 9 contains a pentacene derivative and coordinates the ruthenium fragment at the amidinate moiety thus forming a four-membered chelate ring. Isolation of a second ruthenium complex 8 which contains an intact pyrazino-quinoxaline 6 in which the metal is also coordinated to an amidinato group supports the assumption that the anellation reaction occurs only after metal complexation at the amidinate group. In contrast to this, the smaller [(tmeda)2Pd]2+ fragment reacts with the pyrazino-quinoxaline 6 to form the mononuclear Pd complex 10. Its structural motif (X-ray diffraction) shows that the palladium centre coordinates at the 1,4-diamino group of the intact pyrazino-quinoxaline to form a five-membered chelate ring. This suggests that the bulkiness of the complex fragment determines whether or not an anellation reaction can take place.

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12

Hong, Jin, Gao-Sheng Yang, Chun-Ying Duan, Zi-Jian Guo, and Long-Gen Zhu. "Fluorescence quenching of EB–DNA complex by a novel di-bipyridyl ruthenium(II) complex of p-tert-butyltetrathiacalix[4]arene." Inorganic Chemistry Communications 8, no. 11 (November 2005): 988–91. http://dx.doi.org/10.1016/j.inoche.2005.07.021.

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13

Yu, Hui-Juan, Hui Chao, Long Jiang, Lv-Ying Li, Shu-Mei Huang, and Liang-Nian Ji. "Single oxygen-mediated DNA photocleavage of a di-bithiazolyl ruthenium(II) complex [Ru(btz)2(dppz)]2+." Inorganic Chemistry Communications 11, no. 5 (May 2008): 553–56. http://dx.doi.org/10.1016/j.inoche.2008.02.008.

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14

Losse, Sebastian, Helmar Görls, Robert Groarke, Johannes G. Vos, and Sven Rau. "One-Step Synthesis of 4,4′-Dicyano-2,2′-bipyridine and Its Bis(4,4′-di-tert-butyl-2,2′-bipyridine)ruthenium(II) Complex." European Journal of Inorganic Chemistry 2008, no. 28 (October 2008): 4448–52. http://dx.doi.org/10.1002/ejic.200701304.

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15

Sievertsen, Svend, Hendrik Schlehahn, and Heiner Homborg. "Darstellung, Eigenschaften und elektronische Raman-Spektren von Di(bromo)phthalocyaninatometallaten(III) der Eisengruppe / Synthesis, Properties and Electronic Raman Spectra of Di(bromo)phthalocyaninatometalates(III) of the Iron Group Elements." Zeitschrift für Naturforschung B 49, no. 1 (January 1, 1994): 50–56. http://dx.doi.org/10.1515/znb-1994-0111.

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Abstract Low spin di(bromo)phthalocyaninatometalates of tervalent iron, ruthenium and osmium ([MBr2Pc2-]-) are formed by the reaction of [FeBrPc2-] or H[MBr2Pc2-] (M = Ru, Os) with excess bromide in DMF or THF and isolated as (nBu4N)+ salts. The electronic spectra show the typical π- π*- transitions (B, Q, N region) of the Pc2- ligand together with a number of extra bands due to trip-multiplett and (Pc, Br → M)CT transitions. νs(MBr) is observed in the resonance Raman (RR) spectrum (RR enhanced for M = Fe, Ru) at 161 cm-1 (Fe), 183 cm-1 (Ru) and 192 cm-1 (Os), νas(MBr) at 251 cm-1 (Fe), 234 cm-1 (Ru) and 218 cm-1 (Os) in the FIR spectra. The RR spectra obtained by excitation at low absorbance between the B and Q region are dominated by the intraconfigurational " Γ7 →Γ 8" transition due to spin orbit splitting of the 2T2g ground state for Fe at 583 cm-1, Ru at 1026/1050 cm-1 and Os at 3131 cm-1 . In the MIR resp. NIR spectra vibronically induced transitions are observed for the Ru or Os complex.

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16

Río, Ignacio del, Robert A. Gossage, Milja S. Hannu, Martin Lutz, Anthony L. Spek, and Gerard van Koten. "Synthesis and characterization of two new "pincer" complexes of zinc(II). The X-ray crystal structures of the five coordinate complexes [ZnCl2{η3-NN'N-2,6-(R2NCH2)2C5H3N}] (R = n-Bu or Me)." Canadian Journal of Chemistry 78, no. 12 (December 1, 2000): 1620–26. http://dx.doi.org/10.1139/v00-145.

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The potentially terdentate NN'N donor ligand 2,6-bis[di-(n-butyl)aminomethyl]pyridine (1) does not form a stable, isolable Ru complex using any standard Ru starting materials. This is in contrast to the dimethylamino derivative 2. In the presence of Zn metal as a reducing agent, the treatment of hydrated ruthenium trichloride with 2 leads instead to the isolation of a diamagnetic Zn(II) complex (3) of general formula [ZnCl2(1)]. Analysis of 3 (NMR, X-ray) reveals the complex to be a mononuclear Zn halide compound containing ligand 1 in an η3-NN'N bonding motif. The Zn atom is found to be five-coordinate and in a geometry best described as midway between trigonal bipyramidal and square pyramidal in structure. Similar experiments using 2 produce an analogous Zn species (4) which has likewise been fully characterized (NMR, X-ray) and found to be similar to 3 although the metal is in a distinctly square pyramidal environment. These compounds are viewed as relatives of the class of Zn "pybox" catalysts.Key words: pincer complexes, zinc(II) compounds, X-ray crystal structure.

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17

Chen, Pei-Liang, Hui Chao, Juan Xu, Li Wang, and Hong Li. "Luminescence properties of a di-ruthenium(II) complex with an intramolecular hydrogen bond modulated by DNA and copper(II) ion." Transition Metal Chemistry 34, no. 7 (August 2, 2009): 773–78. http://dx.doi.org/10.1007/s11243-009-9261-5.

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18

Nonomura, Kazuteru, Yunhua Xu, Tannia Marinado, Daniel P. Hagberg, Rong Zhang, Gerrit Boschloo, Licheng Sun, and Anders Hagfeldt. "The Effect of UV-Irradiation (under Short-Circuit Condition) on Dye-Sensitized Solar Cells Sensitized with a Ru-Complex Dye Functionalized with a (diphenylamino)Styryl-Thiophen Group." International Journal of Photoenergy 2009 (2009): 1–9. http://dx.doi.org/10.1155/2009/471828.

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A new ruthenium complex, cis-di(thiocyanato)(2,2′-bipyridine-4,4′-dicarboxylic acid)(4,4′-bis(2-(5-(2-(4-diphenylaminophenyl)ethenyl)-thiophen-2-yl)ethenyl)-2,2′-bipyridine)ruthenium(II) (named E322) has been synthesized for use in dye-sensitized solar cells (DSCs). Higher extinction coefficient and a broader absorption compared to the standard Ru-dye, N719, were aimed. DSCs were fabricated with E322, and the efficiency was 0.12% initially. (4.06% for N719, as reference). The efficiency was enhanced to 1.83% by exposing the cell under simulated sunlight containing UV-irradiation at short-circuit condition. The reasons of this enhancement are (1) enhanceing electron injection from sensitizer toTiO2following a shift toward positive potentials of the conduction band ofTiO2by the adsorption of protons or cations from the sensitizer, or from the redox electrolyte and (2) improving the regeneration reaction of the oxidized dye by the redox electrolyte by the dissolution of aggregated dye from the surface ofTiO2following the treatment.

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19

Furue, Masaoki, Noritaka Kuroda, and Shun-ichi Nozakura. "Synthesis and Luminescence Properties of Di- and Tri-methylene Linked Tris(2,2′-bipyridine)ruthenium(II) Complex Dimers. Ground-Excited State Interaction." Chemistry Letters 15, no. 7 (July 5, 1986): 1209–12. http://dx.doi.org/10.1246/cl.1986.1209.

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20

Savić, Aleksandar, Afya A. Baroud, and Sanja Grgurić-Šipka. "The new ruthenium(II)-bipyridyl complex with O,O'-diethyl-(S,S)-ethylenediamine-N,N'-di-2-(3-cyclohexyl)propanoate: Synthesis and characterization." Macedonian Journal of Chemistry and Chemical Engineering 33, no. 1 (May 2, 2014): 59. http://dx.doi.org/10.20450/mjcce.2014.424.

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<p>The new bipyridyl complex of ruthenium(II) with <em>O,O'</em>-diethyl-(<em>S,S</em>)-ethylenediamine-<em>N,N'</em>-di-2-(3-cyclohexyl)propanoate was synthesized. The reaction of <em>cis</em>-[RuCl<sub>2</sub>(bpy)<sub>2</sub>]<em> </em>and ligand was performed in water/ethanol solution, in the presence of lithium hydroxide, under reflux. The addition of ammonium hexafluorophosphate, complex was precipitated. The complex, <em>cis</em>-[Ru(bpy)<sub>2</sub>L](PF<sub>6</sub>)<sub>2</sub>, was characterized by <sup>1</sup>H and <sup>13</sup>C NMR, UV-Vis, IR spectroscopy, ESI-MS spectrometry and elemental analysis. Results indicate an octahedral geometry of the complex, with <em>N,N'</em>-coordinated <em>O,O'</em>-diethyl-(<em>S,S</em>)-ethylenediamine-<em>N,N'</em>-di-2-(3-cyclohexyl)propanoate. Complexes of this type are particularly important in terms of potential cytotoxicity and application in photodynamic therapy. Using this therapy, many side effects can be reduced and this may allow administration of higher dosages drugs.</p>

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21

Sellmann, Dieter, Christine Rohm, and Matthias Moll. "UbergangsmetalIkomplexe mit Schwefelliganden, CXV+. Protonierung und Alkylierung der Thiolatdonoren von Ru(II)-Komplexen mit [Ru(′buS5′)]-Fragmenten (′buS5–H2 = 2,2′-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsu!fid)/Transition Metal Complexes with Sulfur Ligands, CXV+. Protonation and Alkylation of Thiolate Donors in Ru(II) Complexes with [Ru(′buS5′)] Fragments (′buS5′–H2 = 2,2′-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide)." Zeitschrift für Naturforschung B 50, no. 11 (November 1, 1995): 1729–38. http://dx.doi.org/10.1515/znb-1995-1121.

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Reaction of meso-[Ru(L)(′buS5′)] complexes (L = CO (1), PPh3, PCy3) with one equivalent of oxonium salts R3OBF4 (R = CH3, C2H5) yields the C1 symmetrical monoalkyl derivatives [Ru(L)(′buS5′-R)]BF4 (L = CO, R = CH3 (2), C2H5 (3); L = PPh3, R = CH3 (5); L = PCy3, R = CH3 (6)), in which one of the thiolate donors of the starting complexes is alkylated diastereospecifically. Monoalkylation of the binuclear complex [Ru(′buS5′)]2 leads to C1 symmetrical [Ru(′buS5′-CH3)]2(BF4)2 (7) which gives the hydrazine complex [μ-N2H4{Ru(′buS5′-CH3)}2](BF4)2·N2H4 (9) upon reaction with N2H4.Reaction of 1 with 1.5 equivalents of CF3SO3H yields the isolable thiol complex [Ru(CO)(′buS5′-H)]CF3SO3·0.5 CF3SO3H (4). The 1H-NMR spectra are temperature-dependent and indicate exchange of the thiol proton between the thiolate donors of the ′buS5′2- ligand. Twofold protonation of 1 could only be proved IR-spectroscopically, dialkylation of 1, however, yields isolable [Ru(CO)(′buS5′-(CH3)2)](BF4)2 (8) as a mixture of diastereomers.The IR stretching frequencies ν(CO) of the CO complexes indicate that the electron densities at the ruthenium centers are decreased and the Ru-L bonds are weakened. However, the ligands L in the [Ru(L)(′buS5′-R)]BF4 complexes do not exchange more readily than in the parent complexes.

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22

Bautista, Maria Teresa, Kelly Anne Earl, Patricia Anne Maltby, Robert Harold Morris, and Caroline Theresia Schweitzer. "New dihydrogen complexes: the synthesis and spectroscopic properties of iron(II), ruthenium(II), and osmium(II) complexes containing the meso-tetraphos-1 ligand." Canadian Journal of Chemistry 72, no. 3 (March 1, 1994): 547–60. http://dx.doi.org/10.1139/v94-078.

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The synthesis and properties of dihydrogen complexes trans-[MH(H2)L]+, M = Fe, Ru, Os, which contain the ligand meso-tetraphos-1, S,R-Ph2PCH2CH2P(Ph)CH2CH2P(Ph)CH2CH2PPh2 (L) are described. There are interesting possibilities of isomerism in such trans complexes because the axial binding sites at the metal are different, one being surrounded by four phenyl groups and the other by two phenyl groups. The osmium complex is prepared in an unusual reaction of cis-β-Os(Cl)2L with H2 (1 atm) and NaBPh4 (1 mol) in THF or by the reaction of trans-OsH(Cl)L with NaBPh4 and H2. The iron and ruthenium complexes were made by a reaction of HBF4 with complexes trans-M(H)2L that have inequivalent trans hydrides. The ruthenium complex was also prepared starting from isomers of trans-RuH(Cl)L. The H—H distance in the rapidly spinning dihydrogen ligand has been calculated from T1(min) data to be 0.88, 0.89, and 0.99 Å for the complexes of Fe, Ru, Os, respectively. The presence of the H—D bond in the isotopomers trans-[MH(HD)L]+ and trans-[MD(HD)L]+ is also confirmed by the observation of 1JHD coupling constants of 32, 33.5, and 26.4 Hz for Fe, Ru, and Os, respectively. There is no rapid intramolecular H atom exchange in these complexes in contrast to those with di-tert-phosphine ligands like [MH(H2)(dppe)2]+ or to the trihydride Re(H)3L. Described also are the properties of the precursor complexes including cis-β- and trans-Ru(Cl)2L and derivatives of the dihydrogen complexes trans-[MH(L′)L]+, L′ = CH3CN (on Ru and Os), PMe2Ph (on Ru), and CO (on Os). Trends in the NMR properties of isostructural complexes are reported.

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23

Ohkita, Kenzo, Hideo Asano, Hideo Kurosawa, Toshikazu Hirao, Yohko Miyaji, and Isao Ikeda. "Observation of buttressing effect and hindered rotation about C(sp2)—C(sp2) single bond in styrenes coordinated to a ruthenium cation, Cp(diphosphine)Ru+." Canadian Journal of Chemistry 74, no. 11 (November 1, 1996): 1936–44. http://dx.doi.org/10.1139/v96-220.

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Complexes of (η5-cyclopentadienyl)(bis(di-p-tolylphosphino)ethane)ruthenium(II) cation with some styrenes containing meta or para substituants were prepared and their NMR spectra examined in detail. Variable-temperature NMR studies on the unsubstituted and para-substituted styrene analogues demonstrated occurrence of a restricted rotation about the C(sp2)—C(sp2) single bond of the styrenes where one of the ortho hydrogens of the styrene phenyl group receives a very large diamagnetic shielding effect by one of the phosphine tolyl groups. Similar studies on the meta-substituted styrene complexes showed existence of two unequally populated conformational isomers arising from the similar restricted rotation where the meta substituent in the dominant isomer was placed further away from the C=C group. The origin of such conformational isomerism was deduced to be the buttressing effect of the meta substituent transmitted via the ortho-hydrogen atom. Key words: buttressing effect, hindered rotation, Ru–styrene complex.

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24

Busemann, Anja, Ingrid Flaspohler, Xue-Quan Zhou, Claudia Schmidt, Sina K. Goetzfried, Vincent H. S. van Rixel, Ingo Ott, Maxime A. Siegler, and Sylvestre Bonnet. "Ruthenium-based PACT agents based on bisquinoline chelates: synthesis, photochemistry, and cytotoxicity." JBIC Journal of Biological Inorganic Chemistry 26, no. 6 (August 10, 2021): 667–74. http://dx.doi.org/10.1007/s00775-021-01882-8.

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AbstractThe known ruthenium complex [Ru(tpy)(bpy)(Hmte)](PF6)2 ([1](PF6)2, where tpy = 2,2’:6’,2″-terpyridine, bpy = 2,2’-bipyridine, Hmte = 2-(methylthio)ethanol) is photosubstitutionally active but non-toxic to cancer cells even upon light irradiation. In this work, the two analogs complexes [Ru(tpy)(NN)(Hmte)](PF6)2, where NN = 3,3'-biisoquinoline (i-biq, [2](PF6)2) and di(isoquinolin-3-yl)amine (i-Hdiqa, [3](PF6)2), were synthesized and their photochemistry and phototoxicity evaluated to assess their suitability as photoactivated chemotherapy (PACT) agents. The increase of the aromatic surface of [2](PF6)2 and [3](PF6)2, compared to [1](PF6)2, leads to higher lipophilicity and higher cellular uptake for the former complexes. Such improved uptake is directly correlated to the cytotoxicity of these compounds in the dark: while [2](PF6)2 and [3](PF6)2 showed low EC50 values in human cancer cells, [1](PF6)2 is not cytotoxic due to poor cellular uptake. While stable in the dark, all complexes substituted the protecting thioether ligand upon light irradiation (520 nm), with the highest photosubstitution quantum yield found for [3](PF6)2 (Φ[3] = 0.070). Compounds [2](PF6)2 and [3](PF6)2 were found both more cytotoxic after light activation than in the dark, with a photo index of 4. Considering the very low singlet oxygen quantum yields of these compounds, and the lack of cytotoxicity of the photoreleased Hmte thioether ligand, it can be concluded that the toxicity observed after light activation is due to the photoreleased aqua complexes [Ru(tpy)(NN)(OH2)]2+, and thus that [2](PF6)2 and [3](PF6)2 are promising PACT candidates. Graphic abstract

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25

Yao, Qingwei, and Matthew Sheets. "An ionic liquid-tagged second generation Hoveyda–Grubbs ruthenium carbene complex as highly reactive and recyclable catalyst for ring-closing metathesis of di-, tri- and tetrasubstituted dienes." Journal of Organometallic Chemistry 690, no. 15 (August 2005): 3577–84. http://dx.doi.org/10.1016/j.jorganchem.2005.03.031.

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26

Sellmann, Dieter, Daniel Häußinger, Torsten Gottschalk-Gaudig, and Frank W. Heinemann. "Übergangsmetallkomplexe mit Schwefelliganden, 145 [1]. [Ru(NO)('pybuS4')]Br, ein Komplex mit [Ru(NO)(NS4)]-Gerüst, aktivierten CH2-Gruppen und interionischen Wechselwirkungen im Festkörper ['pybuS4'2- = 2,6-Bis(2-mercapto-3,5-di-terM>utylphenylthio) dimethylpyridin(2-)] / Transition Metal Complexes with Sulfur Ligands, 145 [1]. [Ru(NO)('pybuS4 ')]Br, a Complex with [Ru(NO)(NS4)] Core, Activated CH2 Groups, and Interionic Interactions in the Solid State ('pybuS4'2- = 2,6-Bis(2-mercapto-3,5-di-terf-butylphenylthio)dimethylpyridine(2-))." Zeitschrift für Naturforschung B 55, no. 8 (August 1, 2000): 723–29. http://dx.doi.org/10.1515/znb-2000-0809.

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Abstract In the search for soluble and reactive ruthenium nitrosyl complexes, [Ru(NO)('pybuS4')]Br ([2]Br) was synthesized by template alkylation of NBu4[Ru(NO)('buS2')2] with py(CH2,Br)2 ['pybuS4'2-= 2,6-bis(2-mercapto-3,5-di-tert-butyl-phenylthio)dimethylpyridine(2-); 'buS2'2- = 2-mercapto-3,5-di-tert-butylphenylthiolate(2-); py(CH2Br)2 = 2,6-bis(bromomethyl)pyridine]. The solid state structure of 2 has been determined by X-ray diffraction, which reveals a head-to-head O-O interaction between the linear Ru-NO entities. The ligand CH2 protons of [2]+ are activated and exchange with D+ under ambient conditions. The ν (NO) band of [2]Br appears at 1841 cm-1 in the solid state (KBr or hostaflon mull) and is significantly blue-shifted in solution (1879 cm-1 in MeOH, 1886 cm-1 in DMF). A similar blue-shift (1866 cm-1 in KBr vs. 1888 cm-1 in MeOH) has been found for [Ru(NO)('pyS4')]Br ([1]Br) which contains the parent [Ru(NO)('pyS4')]+ cation ['pyS4'2-= 2,6-bis(2-mercaptophenylthio)dimethylpyridine(2-)]. These ν(NO) shifts can be explained either by an interionic charge-transfer between the bromide anions and the nitrosyl complex cation or by O-O interactions between two NO ligands as found for solid-state [2]Br. These interactions are not found for [1]OTs which exhibits a ν(NO) band at ca. 1890 cm-1 in the solid state (KBr, hostaflon) as well as in MeOH solution.

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27

Sellmann, Dieter, Richard Ruf, Falk Knoch, and Matthias Moll. "Übergangsmetallkomplexe mit Schwefelliganden, CVIII+. Eine bequeme Synthese des tertiären Amin-thiolat-Liganden 'S2N2Me2'2-. Einfluß der Aminmethylierung auf die Koordinationschemie von Nickel- und Ruthenium-Komplexen mit [M('S2N2R2')]-Geriisten (R = H, CH3). ('S2N2Me2'2- = 1,2-Ethandiamin-N,N'-dimethyl-N,N'-bis(2-benzolthiolat)(2-)) / Transition Metal Complexes with Sulfur Ligands, CVIII+. A Facile Synthesis of the Tertiary Amine-thiolato Ligand 'S2N2Me2'2-. Influence of the Aminomethylation on the Coordination Chemistry of Nickel and Ruthenium Complexes with [M('S2N2R2')] Frameworks (R = H, CH3). ('S2N2Me2'2- = 1,2-Ethanediamino-N,N'-dimethyl-N,N'-bis(2-benzenethiolato)(2-))." Zeitschrift für Naturforschung B 50, no. 5 (May 1, 1995): 791–801. http://dx.doi.org/10.1515/znb-1995-0518.

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Abstract In a single pot synthesis consecutive reaction of the tetradentate amine-thiole H2-'S2N2H2' 2 ('S2N2H2'2- = 1,2-ethanediamino-N,N'-bis(2-benzenethiolato)(2-)). with [LiN(SiMe3)2] and benzyl chloride (BzCl) yields the amine-thioether 'Bz2S2N2H2' which gives the tertiary amine-thioether 'Bz2S2N2Me2' when reacted with further [LiN(SiMe3)2] and CH3I Removal of the benzyl groups with an excess of sodium and acidification with hydrochloric acid finally yield H2-'S2N2Me2' I ('S2N2Me2'2- = 1,2-ethanediamino-N,N'-di- methyl-N,N'-bis(2-benzenethiolato)(2-)). 1 and 2 have been characterized by X-ray structure analysis. With [Ni(CH3COO)2] · 4H2O,1 yields racemic [Ni('S2N2Me2')] 3 in a diastereospecific reaction. Crystallization of 3 leads to spontaneous resolution of the racemate. By X-ray structure analysis of 3 the absolute configuration in the single crystal examined was determined using Roger's μ-refinement (μ = 1.00(4)). Upon reaction with [RuCl3·3H2O]. LiOMe and CO. I yields [Ru(CO)2('S2N2Me2')] 5. Spectroscopic data indicate that 5 and the parent complex [Ru(CO)2('S2N2H2')] differ with respect to their core structures. Influence of the amine methylation on structure and reactivity of complexes with [M('S2N2R2')] cores, R = H. Me, is discussed.

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28

Martínez-Alonso, Marta, and Gilles Gasser. "Ruthenium polypyridyl complex-containing bioconjugates." Coordination Chemistry Reviews 434 (May 2021): 213736. http://dx.doi.org/10.1016/j.ccr.2020.213736.

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29

Barral, M. Carmen, Santiago Herrero, Reyes Jiménez-Aparicio, M. Rosario Torres, and Francisco A. Urbanos. "A Spin-Admixed Ruthenium Complex." Angewandte Chemie International Edition 44, no. 2 (December 21, 2004): 305–7. http://dx.doi.org/10.1002/anie.200461463.

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30

Gómez-Lor, Berta, Amelia Santos, Marta Ruiz, and Antonio M. Echavarren. "Ruthenium-Capping of Di- and Tetraethynylbiphenyls." European Journal of Inorganic Chemistry 2001, no. 9 (September 2001): 2305–10. http://dx.doi.org/10.1002/1099-0682(200109)2001:9<2305::aid-ejic2305>3.0.co;2-t.

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31

Bernhard, Paul, and Alan M. Sargeson. "Stepwise dehydrogenation of a ruthenium(III) hexaamine cage complex to a hexaimine ruthenium(II) complex via ruthenium(IV) intermediates." Journal of the American Chemical Society 111, no. 2 (January 1989): 597–606. http://dx.doi.org/10.1021/ja00184a030.

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32

Mattsson, Johan, and Bruno Therrien. "Di-μ-chlorido-bis[chlorido(η6-toluene)ruthenium(II)]." Acta Crystallographica Section E Structure Reports Online 63, no. 11 (October 19, 2007): m2757. http://dx.doi.org/10.1107/s1600536807050544.

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In the centrosymmetric dinuclear title complex, [Ru2Cl4(η6-C6H5CH3)2], accessible from RuCl3·nH2O and 1-methylcyclohexa-1,4-diene, the toluene ligand is planar with a ruthenium–centroid distance of 1.646 Å.

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33

Ito, Yuta. "Development of Ruthenium Complex-Conjugated Oligonucleotides." Journal of Synthetic Organic Chemistry, Japan 78, no. 9 (September 1, 2020): 898–900. http://dx.doi.org/10.5059/yukigoseikyokaishi.78.898.

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34

Mirza, Hameed A., Jagadese J. Vittal, and Richard J. Puddephatt. "A BINUCLEAR ALKYNE COMPLEX OF RUTHENIUM." Journal of Coordination Chemistry 37, no. 1-4 (February 1, 1996): 131–39. http://dx.doi.org/10.1080/00958979608023546.

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35

Sugimoto, Hideki, Kazunobu Sato, Takeji Takui, and Koji Tanaka. "Unprecedented Sequential Deprotonation of Ruthenium–Aqua Framework Affording Ruthenium–Oxo–Dithiolene Complex." Chemistry Letters 33, no. 9 (September 2004): 1082–83. http://dx.doi.org/10.1246/cl.2004.1082.

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36

Huang, Wen-Lin, Guan-Jie Hung, and Yih-Hsing Lo. "Unprecedented formation of ruthenium 2-mercaptobenzothiazole complex." Journal of Organometallic Chemistry 767 (September 2014): 120–24. http://dx.doi.org/10.1016/j.jorganchem.2014.05.010.

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37

Vieille-Petit, Ludovic, Bruno Therrien, and Georg Süss-Fink. "An asymmetric trihydrido-bridged arene ruthenium complex." Inorganic Chemistry Communications 7, no. 2 (February 2004): 232–34. http://dx.doi.org/10.1016/j.inoche.2003.10.026.

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38

Irvoas, Joris, Arielle Noirot, Nadia Chouini-Lalanne, Olivier Reynes, and Valerie Sartor. "DNA three-way junction–ruthenium complex assemblies." New Journal of Chemistry 37, no. 8 (2013): 2324. http://dx.doi.org/10.1039/c3nj00288h.

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39

Mitsudo, Take-aki, Nobuyoshi Suzuki, Teruyuki Kondo, and Yoshihisa Watanabe. "Ruthenium Complex-Catalyzed Carbonylation of Allylic Compounds." Journal of Organic Chemistry 59, no. 25 (December 1994): 7759–65. http://dx.doi.org/10.1021/jo00104a036.

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40

Dragutan, Ileana, Valerian Dragutan, and Albert Demonceau. "Editorial of Special Issue Ruthenium Complex: The Expanding Chemistry of the Ruthenium Complexes." Molecules 20, no. 9 (September 18, 2015): 17244–74. http://dx.doi.org/10.3390/molecules200917244.

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41

Jimenez, Jorge, Indranil Chakraborty, and Pradip Mascharak. "Synthesis and structures of ruthenium di- and tricarbonyl complexes derived from 4,5-diazafluoren-9-one." Acta Crystallographica Section C Structural Chemistry 71, no. 11 (October 13, 2015): 965–68. http://dx.doi.org/10.1107/s2053229615018100.

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Carbon monoxide (CO) has recently been shown to impart beneficial effects in mammalian physiology and considerable research attention is now being directed toward metal–carbonyl complexes as a means of delivering CO to biological targets. Two ruthenium carbonyl complexes, namelytrans-dicarbonyldichlorido(4,5-diazafluoren-9-one-κ2N,N′)ruthenium(II), [RuCl2(C11H6N2O)(CO)2], (1), andfac-tricarbonyldichlorido(4,5-diazafluoren-9-one-κN)ruthenium(II), [RuCl2(C11H6N2O)(CO)3], (2), have been isolated and structurally characterized. In the case of complex (1), thetrans-directing effect of the CO ligands allows bidentate coordination of the 4,5-diazafluoren-9-one (dafo) ligand despite a larger bite distance between the N-donor atoms. In complex (2), thecisdisposition of two chloride ligands restricts the ability of the dafo molecule to bind ruthenium in a bidentate fashion. Both complexes exhibit well defined1H NMR spectra confirming the diamagnetic ground state of RuIIand display a strong absorption band around 300 nm in the UV.

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42

de Carvalho, Idalina M. M., Ícaro de Sousa Moreira, and Marcelo H. Gehlen. "The amide bridge photocleavage in ruthenium bichromophoric complex." Inorganica Chimica Acta 358, no. 7 (April 2005): 2255–61. http://dx.doi.org/10.1016/j.ica.2005.01.012.

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43

Liu, Shi-Xia, Antonia Neels, Helen Stoeckli-Evans, and Silvio Decurtins. "A New Luminescent and Redox-Active Ruthenium Complex." Phosphorus, Sulfur, and Silicon and the Related Elements 180, no. 5-6 (March 2, 2005): 1469–70. http://dx.doi.org/10.1080/10426500590913168.

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44

Feichtner, Kai-Stephan, Florian Papp, Michelle Schmidt, Maurice Paaßen, and Viktoria H. Gessner. "Carbene complex formation versus cyclometallation from a phosphoryl-tethered methanide ruthenium complex." Journal of Organometallic Chemistry 915 (June 2020): 121235. http://dx.doi.org/10.1016/j.jorganchem.2020.121235.

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45

KAMIGATA, Nobumasa, and Masayuki KAMEYAMA. "Highly selective radical reactions catalyzed by ruthenium complex." Journal of Synthetic Organic Chemistry, Japan 47, no. 5 (1989): 436–47. http://dx.doi.org/10.5059/yukigoseikyokaishi.47.436.

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46

Tanaka, Hirotaka, Kentaro Hashimoto, Kyosuke Suzuki, Yasunori Kitaichi, Mitsuo Sato, Taketo Ikeno, and Tohru Yamada. "Nitrous Oxide Oxidation Catalyzed by Ruthenium Porphyrin Complex." Bulletin of the Chemical Society of Japan 77, no. 10 (October 2004): 1905–14. http://dx.doi.org/10.1246/bcsj.77.1905.

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47

Rau, Sven, Matthias Schwalbe, Sebastian Losse, Helmar Görls, Cale McAlister, Frederick M. MacDonnell, and Johannes G. Vos. "Photoinduced Ligand Transformation in a Ruthenium Polypyridophenazine Complex." European Journal of Inorganic Chemistry 2008, no. 7 (March 2008): 1031–34. http://dx.doi.org/10.1002/ejic.200700947.

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48

Maji, Milan, and Sabuj Kundu. "Cooperative ruthenium complex catalyzed multicomponent synthesis of pyrimidines." Dalton Transactions 48, no. 47 (2019): 17479–87. http://dx.doi.org/10.1039/c9dt04040d.

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49

Bruce, Michael I., Mark A. Fox, Paul J. Low, Brian W. Skelton, and Natasha N. Zaitseva. "Some reactions of an η3-tetracyanobutadienyl-ruthenium complex." Dalton Transactions 39, no. 15 (2010): 3759. http://dx.doi.org/10.1039/b921324d.

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50

McClure, Beth Anne, and Jeffrey J. Rack. "Ultrafast Spectroscopy of a Photochromic Ruthenium Sulfoxide Complex." Inorganic Chemistry 50, no. 16 (August 15, 2011): 7586–90. http://dx.doi.org/10.1021/ic200532p.

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