Tesis: "Ruthenium"

1

Barth, Michael. "Polyolato-Komplexe mit Ruthenium(II), Ruthenium(VI) und Osmium(VI)". Diss., lmu, 2005. http://nbn-resolving.de/urn:nbn:de:bvb:19-43966.

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2

Taylor, Daniel M. "Electrochemical Depostion of Bismuth on Ruthenium and Ruthenium Oxide Surfaces". Thesis, University of North Texas, 2012. https://digital.library.unt.edu/ark:/67531/metadc115169/.

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Cyclic voltammetry experiments were performed to compare the electrodeposition characteristics of bismuth on ruthenium. Two types of electrodes were used for comparison: a Ru shot electrode (polycrystalline) and a thin film of radio-frequency sputtered Ru on a Ti/Si(100) support. Experiments were performed in 1mM Bi(NO3)3/0.5M H2SO4 with switching potentials between -0.25 and 0.55V (vs. KCl sat. Ag/AgCl) and a 20mV/s scan rate. Grazing incidence x-ray diffraction (GIXRD) determined the freshly prepared thin film electrode was hexagonally close-packed. After thermally oxidizing at 600°C for 20 minutes, the thin film adopts the tetragonal structure consistent with RuO2. a hydrated oxide film (RuOx?(H2O)y) was made by holding 1.3V on the surface of the film in H2SO4 for 60 seconds and was determined to be amorphous. Underpotential deposition of Bi was observed on the metallic surfaces and the electrochemically oxidized surface; it was not observed on the thermal oxide.

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3

Keceli, Ezgi. "Ruthenium(iii) Acetylacetonate". Master's thesis, METU, 2006. http://etd.lib.metu.edu.tr/upload/3/12607230/index.pdf.

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Ruthenium(III) acetylacetonate was employed for the first time as homogeneous catalyst in the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was not reduced by sodium borohydride under the experimental conditions and remains unchanged after the catalysis, as shown by FT-IR and UV-Vis spectroscopic characterization. Poisoning experiments with mercury, carbon disulfide or trimethylphosphite provide compelling evidence that ruthenium(III) acetylacetonate is indeed a homogenous catalyst in the hydrolysis of sodium borohydride. Kinetics of the ruthenium(III) acetylacetonate catalyzed hydrolysis of sodium borohydride was studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first order with respect to both the substrate concentration and catalyst concentration. The activation parameters of this reaction were also determined from the evaluation of the kinetic data: activation energy
Ea = 25.6 &
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1.3 kJ.mol-1, the enthalpy of activation
&
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1.2 kJ.mol-1 and the entropy of activation &
#8710
S# = -170 ±
5 J&
#61655
mol-1&
#61655
K-1. Ruthenium(III) acetylacetonate provides the lowest activation energy ever found for the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was found to be highly active catalyst providing 1183 total turnovers in the hydrolysis of sodium borohydride over 180 min before they are deactivated. The recorded turnover frequency (TOF) is 6.55 min-1.

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4

Bates, Richard Simon. "Arene ruthenium chemistry". Thesis, University of Nottingham, 1990. http://eprints.nottingham.ac.uk/11890/.

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This thesis describes the synthesis and reactivity studies of new arene-ruthenium(II) and arene-ruthenium(O) complexes. Ultrasound has been investigated as an alternative energy source, with the overall aim of synthesising arene ruthenium clusters. Chapter 1 gives an introduction and summary of the known arene ruthenium chemistry reported to date. Chapter 2 reports the synthesis of (CGH6)Ru(C2H4)2 and (MeC6H4CHMe2)Ru(C2H4)2. Low temperature protonation studies generated (C6H6)Ru(H)(CZH4)2' and (MeC6H4CHMe2)Ru(H)(C2H4)7ý. These are observed by 1H nmr spectroscopy to undergo two dynamic processes, rotation of the ethylene ligands and an exchange between the hydride and the hydrogens of the ethylenes. On protonation with trifluoroacetic acid (C6H6)Ru(02CCF3)2 has been shown to be the final product. Nucleophilic substitution investigations of the bis(ethylene) complexes has determined that the arene is more labile than the coordinated ethylene. Chapter 3 reports the generation of a reactive intermediate, [(MeC6H4CHMez)Ru(THF)2]", and the reactions it undergoes. The synthesis and stereochemistry of the new complexes [(MeC6H4CHMe2)RuBr(C3H5)] and Ru(H)[(C6H40) (OPh)2][P(OPh)3]3 are reported. Chapter 4 describes the successful synthesis of the project goal, with the formation of the trimer [(MeC. H., CHMe2)3Ru3Se,_1` and the tetra nuclear species [(MeC6H4CHMe2)4Ru4H4]2'. Electrochemistry shows both complexes undergo two, one-electron reversible reductions to generate their neutral analogues. Ru3(CO)12 was formed when arene ruthenium carbonyl clusters were sought. Chapter 5 reports the formation and reactivity of arene ruthenium complexes containing nitrogen based ligands. The half sandwich complexes, (arene)RuCl2(NH2R) (arene = C6H6, R= Et, CMe, C6H4Me; McC6H4CHMe2, R=CMe3) and (C. H6)RuCl(NHZCGH4Me)Z' have been synthesised in good yield. However, these complexes are not synthetically useful as substrates for cluster synthesis, although (C6H6)RuC12(NH2CMe3) can be converted to the mixed ethoxide-halide dimer, [(C6H6)Ru(OEt)]2Cl`. Me3SiN3 on reaction with [(MeC6H4CHMe2)RuC12]2 affords [(MeC6H4CHMe2)RuCl(N3)]Z. An X-ray crystal structure determination of this complex showed the nitrogens bridging the two ruthenium atoms are pyramidal rather than the expected planar in geometry. [(MeC6H4CHMe2)RuCl(N3)]2 undergoes chloride loss to form the triply bridged dimer, [(MeCGH4CHMe2)RuCl(N3)z]', and bridge cleavage to form [(MeC, H4CHMe2)RuCl(N3)PPh3]. The latter complex is believed to undergo disproportionation in solution. Conclusions and future directions of the project are discussed in chapter. 6. The appendix provides a discussion of ultrasound proposed structure.

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5

Smith, Paul David. "Arene-ruthenium chemistry". Thesis, University of Nottingham, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.357040.

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6

Dutton, Tom. "Ruthenium carbido clusters". Thesis, University of Cambridge, 1989. https://www.repository.cam.ac.uk/handle/1810/290027.

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7

Stemmler, Marco. "Ruthenium-Thiozimtaldehyd-Komplexe". Doctoral thesis, [S.l. : s.n.], 2002. https://nbn-resolving.org/urn:nbn:de:bvb:20-opus-4050.

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Der erste Teil der vorliegenden Arbeit befasst sich mit der Darstellung neuer achiraler und chiraler kationischer Ruthenium-Bis(phosphan)-Thiozimtaldehyd-Komplexe. Die Umsetzung der chiralen Hydrogensulfid-Komplexe mit unterschiedlich substituierten Zimtaldehyden in Anwesenheit von Trifluoressigsäure führt zu den chiralen Thiozimtaldehyd-Komplexen. Im zweiten Teil dieser Arbeit wird gezeigt, dass Thiozimtaldehyd-Komplexe bereitwillig Hetero-Diels-Alder-Reaktionen eingehen. Derartige Reaktionen können mit freien Vertretern dieser Spezies aufgrund deren Instabilität nur schwierig durchgeführt werden. Der dritte Teil der vorliegenden Arbeit befasst sich mit Cycloadditionsreaktionen der Thiozimtaldehyd-Komplexe mit 1,3-dipolaren Reagenzien. In einem weiteren Teil dieser Arbeit wird die Abspaltung der Thioether-Liganden vom Komplexfragment untersucht
The first part of the present work deals with the synthesis of new achiral and chiral cationic Ru-bis(phosphane)-thiocinnamaldehyde complexes. The reaction of the chiral hydrogensulfido complexes with various substituted cinnamaldehydes in the presence of trifluoroacetic acid gives the chiral thiocinnamaldehyde complexes. In the second part of this work it is demonstrated that the thiocinnamaldehyde complexes readily undergo hetero-Diels-Alder-reactions. The third part of this work deals with cycloaddition reactions of thiocinnamaldehyde complexes with 1,3 dipolar molecules. In a further part of this work the elimination reactions of the thiopyran ligands from the complex fragments are examined

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8

Liao, Wen, Daniel Bost y John G. Ekerdt. "Growth of Ultra-thin Ruthenium and Ruthenium Alloy Films for Copper Barriers". Universitätsbibliothek Chemnitz, 2016. http://nbn-resolving.de/urn:nbn:de:bsz:ch1-qucosa-207151.

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We report approaches to grow ultrathin Ru films for application as a seed layer and Cu diffusion barrier. For chemical vapor deposition (CVD) with Ru3(CO)12 we show the role surface hydroxyl groups have in nucleating the Ru islands that grow into a continuous film in a Volmer-Weber process, and how the nucleation density can be increased by applying a CO or NH3 overpressure. Thinner continuous films evolve in the presence of a CO overpressure. We report an optimun ammonia overpressure for Ru nucleation and that leads to deposition of smoother Ru thin films. Finally, we report a comparison of amorphous Ru films that are alloyed with P or B and demonstrate 3-nm thick amorphous Ru(B) films function as a Cu diffusion barrier.

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9

Kim, Young Dok. "Atomic scale structure and catalytic reactivity of RuO2". [S.l. : s.n.], 2000. http://www.diss.fu-berlin.de/2000/121/index.html.

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10

Denzler, Daniel N. "Zur ultraschnellen Reaktionsdynamik von Wasserstoff und Grenzflächenstruktur von Wasser auf der Ru(001)-Oberfläche". [S.l. : s.n.], 2003. http://www.diss.fu-berlin.de/2003/178/index.html.

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11

Currie, Robert Bruce. "Luminescent Cyclometalated Ruthenium Complexes". Thesis, University of Canterbury. Chemistry, 2015. http://hdl.handle.net/10092/10769.

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This thesis describes the synthesis and structural characterisation of cyclometalated heteroleptic bis(tridentate)ruthenium(II) complexes based on [Ru(terpyridine)(1,3-dipyridylbenzene)]PF6, a cyclometalated analogue of [Ru(terpyridine)2](PF6)2. These complexes are investigated photophysically, photochemically and electrochemically, and also studied by computational methods. Electron donating, electron withdrawing and large aryl groups have been incorporated at three different positions, and pyrazol-1-yl or 1,2,3-triazol-4-yl used as the N-heterocycle instead of 2-pyridyl groups, as in the parent complex, [Ru(terpyridine)(1,3-dipyridylbenzene)]PF6. The ligands are substituted at the 4 position of the central benzene or pyridine ring, or attached to the N-heterocycle. The positions of these modifications have been specifically chosen to direct electronic effects into the Ru-C bond, the opposite Ru-N bond or directly into the N-heterocycle to analyze their effect. This has provided an understanding as to which stereoelectronict features are most important with regards to changing the electronic nature of the complex, and thus tuning the properties of these complexes. This proves particularly effective in analysing the energy of the visible absorptions resulting from metal-to-ligand charge transfer and emission energy and its related quantum yield.

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12

Morris, James Alan. "Palladium-ruthenium bimetallic cascades". Thesis, University of Leeds, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.405707.

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13

Bearman, Philip Stephen. "Rhodium ruthenium heterobimetallic complexes". Thesis, University of Liverpool, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.295827.

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14

Dyson, Paul J. "Arene clusters of ruthenium". Thesis, University of Edinburgh, 1993. http://hdl.handle.net/1842/13755.

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The thesis commences with a general introduction outlining the attraction of arene clusters and develops the area pertinent to the research described thereafter. An account of the synthesis, characterisation and reactivity of a series of cyclohexadiene and benzene clusters derived from the pentanuclear cluster Ru₅C(CO)₁₅ is given. Encompassed within this work are investigations concerned with benzene migration and mechanisms by which 1,4-dienes isomerise to 1,3-dienes. A new stepwise route to the bis-benzene cluster Ru₆C(CO)₁₁(η⁶-C₆H₆)(μ₃-η²:η²:η²-C₆H₆) is described, followed by a more general route to bis-arene clusters. Chemical characterisation and structural elucidation of a range of intermediate compounds and other arene and bis-arene species are chronicled. These include 'sandwich' clusters and a face-capping arene in a near-ecliped orientation. The five-membered aromatic ring systems [C₅Me₅]^- and [C₅H₅]^- are also described. Lastly, the crystal structures exhibited by arene clusters are examined. A co-crystal containing both a mono- and bis-arene species shows that the interactions found in independent crystals also dominate in the mixed system.

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15

Keep, Ann Kathleen. "Ruthenium boron cluster chemistry". Thesis, University of Cambridge, 1990. https://www.repository.cam.ac.uk/handle/1810/272941.

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16

Choi, Kwok-wai Matthew y 蔡國偉. "Carbenoid transfer reactions catalyzed by arene ruthenium complexes and polymer supported ruthenium catalysts". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2008. http://hub.hku.hk/bib/B4088773X.

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17

Lim, ChangDuk. "Materials properties of ruthenium and ruthenium oxides thin films for advanced electronic applications". Thesis, University of North Texas, 2006. https://digital.library.unt.edu/ark:/67531/metadc5592/.

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Ruthenium and ruthenium dioxide thin films have shown great promise in various applications, such as thick film resistors, buffer layers for yttrium barium copper oxide (YBCO) superconducting thin films, and as electrodes in ferroelectric memories. Other potential applications in Si based complementary metal oxide semiconductor (CMOS) devices are currently being studied. The search for alternative metal-based gate electrodes as a replacement of poly-Si gates has intensified during the last few years. Metal gates are required to maintain scaling and performance of future CMOS devices. Ru based materials have many desirable properties and are good gate electrode candidates for future metal-oxide-semiconductor (MOS) device applications. Moreover, Ru and RuO2 are promising candidates as diffusion barriers for copper interconnects. In this thesis, the thermal stability and interfacial diffusion and reaction of both Ru and RuO2 thin films on HfO2 gate dielectrics were investigated using Rutherford backscattering spectrometry (RBS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). An overview of Ru and RuO2/HfO2 interface integrity issues will be presented. In addition, the effects of C ion modification of RuO2 thin films on the physico-chemical and electrical properties are evaluated.

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18

Choi, Kwok-wai Matthew. "Carbenoid transfer reactions catalyzed by arene ruthenium complexes and polymer supported ruthenium catalysts". Click to view the E-thesis via HKUTO, 2008. http://sunzi.lib.hku.hk/hkuto/record/B4088773X.

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19

Wong, Kwok-ming y 黃國明. "Ruthenium-nitrogen and ruthenium-phosphorus multiple bonds supported by phthalocyanines: syntheses, spectroscopicproperties, and reactivities". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2010. http://hub.hku.hk/bib/B45545893.

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20

Chan, Peter Ka-Lin. "Ruthenium nitroimidazole complexes as radiosensitizers". Thesis, University of British Columbia, 1988. http://hdl.handle.net/2429/28639.

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Local control of tumours by radiotherapy may fail due to the presence of regions of hypoxic cells. Radiosensitizers, such as nitroimidazoles, enhance killing of the resistant cells by ionizing radiation. However, dose limiting side-effects have prevented the attainment of maximum sensitization. The successful chemotherapeutic drug, cis-diamminedichloroplatinum(II) (cis-DDP), and analogues show moderate radiosensitizing effects, possibly because of binding to DNA. A rationale is then to use the DNA binding property of a metal to carry a sensitizer to the target of radiation damage, DNA, thereby improving the radiosensitizing effect while reducing the toxic side-effects of nitroimidazoles. The complex cis-RuCI₂(dmso)₄ was used as a precursor for synthesis of Ru(II)-nitroimidazole complexes because of its anti-tumour and DNA binding activities. A series of Ru(II) complexes of formulation RuCI₂(dmso)₂Ln, where dmso is S-bonded dimethyl sulphoxide, L = a nitroimidazole, and n=1 or 2, has been synthesized and characterized, and their toxicities and radiosensitizing abilities examined in vitro. When L = 2-nitroimidazole or a substituted-2-nitroimidazole, n = 2, but the nitroimidazole ligands dissociate in aqueous medium. With L = the 5-nitroimidazole, metronidazole, n=2, the sensitizing ability of the six-coordinate cis complex was disappointing with sensitizer enhancement ratio (SER) of 1.2 in hypoxic Chinese hamster ovary (CHO) cells. A series of 4-nitroimidazoles ligands was then studied. With L = 4-nitroimidazole (4-NO₂-Im), 1-(1' -aziridinyl-2' -propanol)-2-methyl-4-nitroimidazole (RSU-1170), 2-(1,2-dimethyl-4-nitroimidazolyl)-2-aminoethanol (RSU-3083), and 1-methyl-4-nitro-5-phenoxyimidazole (RSU-3100), n=2 and the six coordinate complexes appear to be of all cis geometry. The NMe-4-NO₂-Im ligand (n=1) chelates through the imidazole-N and the oxygen of NO₂ group as evidenced from spectroscopic data. Coordination via the nitrito group is uncommon and other examples involving nitroimidazole ligands have not been reported. For the 1-methyl-5-(2'-thioimidazolyl)-4-nitroimidazole (RSU-3159) ligand (n=1), binding to Ru occurs through the thioether and chelation may occur through the imidazole-NCH₃. In this series of Ru(II)-4-nitroimidazole complexes studied, RuC1₂(dmso)₂-NO₂-Im)₂, 5, was the most effective radiosensitizer (SER = 1.6 at 200 ,μM) and is better than the clinically used misonidazole (SER = 1.3 at 200 μM). In addition, 5 did not sensitize oxic CHO cells. Other Ru-N-substituted-4-nitroimidazole complexes gave SER values of 1.1-1.4 at 100-200 μM. Complex 5 also produced a dose-dependent increase in genotoxic activity (as measured by the in vitro induction of chromosome aberrations in CHO cells), which is similar to that of misonidazole but much less than that of c/s-DDP. Two changes in ancillary ligands and geometry of complexes were also examined: replacement of (i) dmso by tmso (tetramethylene sulphoxide), (ii) C1⁻ by Br⁻. The Ru-nitroimidazole complexes were synthesized from the precursors RuCl₂(tmso)₄ and trans-RuBr₂(dmso)₄. In this series of complexes, only RuCl₂(tmso)₂(4-NO₂-Im)₂, 15, and RuCl₂(tmso)₂(SR-2508), 18, have significantly higher SER values (1.6 and 1.5, respectively) than their corresponding nitroimidazole ligands. The tmso complexes of 2-NO₂-Im derivatives were more stable than the dmso series in aqueous solution with respect to the dissociation of the nitroimidazole ligands, which might be due to the improved lipophilicity of tmso complexes. Complex 18. is suggested to be penta-coordinated from XPS and ir data. The RuBr₂(dmso)₂(4-NO₂-Im)₂ was a less effective sensitizer (SER = 1.3 at 200 μM) than the dichloro analogue which may result from different geometrical structures or different behaviour in aqueous solution chemistry. The enhanced radiosensitizing effect over the corresponding free nitroimidazole ligand observed for complexes 5, 15 and 18 may depend on: (a) the metal's ability to target the sensitizer to DNA; complex 5 does bind to DNA, dissociation of C1⁻ perhaps facilitating the reaction; (b) the increase in reduction potential or (c) an increase in lipophilicity of the nitroimidazole ligand on coordination. However, the enhanced radiosensitization does not result from depletion of non-protein thiols. In the present study, the Ru complexes are less toxic than their corresponding nitroimiazole ligands in vitro. The radiosensitization and toxicity of the complexes 5, 15 and 18 are better than those of the free nitroimidazole ligands and the clinically used radiosensitizer, misonidazole. The data encourage further investigations of the use of transition metal complexes as radiosensitizers to combat the hypoxic tumour cells. [Formula Omitted]
Science, Faculty of
Chemistry, Department of
Graduate

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21

Krasik, Pavel. "Asymmetric ruthenium catalyzed reduction reactions". Thesis, University of Ottawa (Canada), 1994. http://hdl.handle.net/10393/6562.

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22

Hooper, Andrew David. "Alkane hydrogenolysis on ruthenium catalysts". Thesis, Brunel University, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302574.

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23

Knowles, Daniel R. T. "Ruthenium complexes bearing pendent arms". Thesis, University of Sheffield, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.286874.

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24

Nagle, K. R. "Reactions of (tetraphenylcyclobutadiene) ruthenium complexes". Thesis, University of Bristol, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.379549.

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25

Finnegan, David Francis. "Tandem Reactions Involving Ruthenium Alkylidenes". Thesis, Boston College, 2009. http://hdl.handle.net/2345/728.

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Thesis advisor: Marc L. Snapper
Tandem Reactions have proven themselves to be useful reactions for the synthesis of highly complex materials. Ruthenium alkylidenes are shown to be useful precursors for the development of new tandem processes. First, a new tandem metathesis/hetero-Pauson-Khand process is developed using Grubbs' second generation catalyst. Next, various metatheis/olefin isomerization processes are explored
Thesis (PhD) — Boston College, 2009
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry

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26

Bugarcic, Tijana. "Ruthenium arene anti-cancer complexes". Thesis, University of Edinburgh, 2008. http://hdl.handle.net/1842/13265.

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This thesis is concerned with the synthesis and characterization of novel Ru^II arene anti-cancer complexes, containing different arenes and chelating ligands, especially arenes that can act as intercalators and chelating ligands that are redox-active. Synthesis and characterization of complexes of the type [(H⁶-arene)Ru(en)Cl]⁺, where the arene is ortho-, meta- or para-terphenyl (o-, m- or p-terp) are reported. [(H⁶-p-terp)Ru(en)Cl]⁺ has a similar potency to cisplatin and much higher activity against cancer cell lines than o- and m-terp analogues. The p-terp complex binds to DNA rapidly and quantitatively and the experimental data are consistent with combined intercalative and monofunctional (coordination) binding mode of [(H⁶-p-terp)Ru(en)Cl]⁺. The o- and m-terp analogues bind to DNA preferentially through coordination of ruthenium. The synthesis and characterization of Ru^II arene complexes containing 2,2’-bipyridine (bipy), 2,2’-bipyridine-3,3’-diol (bipy(OH)₂) or deprotonated 2,2’-bipyridine-3,3’-diol (bipy(OH)O) as chelating ligands and different arenes are reported, including several x-ray crystal structures. In aqueous solution only the deprotonated (bipy(OH)O) form of the 2,2’-bipyridine-3,3’-diol is present in the complexes. Hydrolysis of these complexes in aqueous solution is relatively fast (37°C) and when the arene is biphenyl, initial aquation is followed by partial arene loss. Complexes with bipy(OH)O as chelating ligands, in general exhibit good cytotoxicity towards A2780 human ovarian cancer cells. Oxidation of the o-phenylenediamine (o-pda) chelating ligand in [(H⁶-arene)Ru(o-pda)Cl]⁺ to o-benzoquinonediimine (o-bqdi) leads to loss of cytotoxic activity. The x-ray crystal structures of [(H⁶-p-cym)Ru(o-pda)Cl][PF₆] and [(H⁶-hmb)Ru(o-bqdi)Cl][PF₆] are reported.

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27

Dougan, Sarah J. "Ruthenium arene azo anticancer complexes". Thesis, University of Edinburgh, 2007. http://hdl.handle.net/1842/13699.

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This thesis is concerned with the design of ruthenium(II) arene anticancer complexes where the chelating ligand contains an azo-imine group (N=N-C=N) which binds to the ruthenium to form a five-membered chelate ring. Several mononuclear complexes containing the chelating 2-phenylazopyridine ligand or derivatives thereof were found to be moderately cytotoxic towards A2780 human ovarian and A549 human lung cancer cells (IC₅₀ 18-88 μM). These complexes were found to hydrolase (Ru-C1 → Ru-OH₂) slowly in aqueous solution and arene loss was a competing reaction. X-ray crystal structures revealed that the arene ligand is not as tightly bound to the ruthenium as in the case when the chelating ligand is en. Synthesis of the corresponding dinuclear analogues, where two 2-phenylazopyridine ligands were joined together via a linker, did not improve the cytotoxicity. Unlike their mononuclear analogues, the complexes appeared to undergo electrochemical reduction with radical formation in aqueous solution. An EPR spectrum of the mono-reduced anion revealed an entirely ligand based radical. Surprisingly, replacement of Cl^- by I^- in the mononuclear complexes led to compounds that were highly cytotoxic towards both A2780 and A549 cancer cells (IC₅₀ 1-5 μM). Interestingly these complexes were resistant to hydrolysis in aqueous solution suggesting that this class of compounds had a novel mechanism of cytotoxic action not involving activation by hydrolysis. The redox chemistry of these complexes proved to be central to their observed cytotoxicity. The complexes were rapidly reduced by the biological reductant ascorbate, catalytically oxidised the tripeptide glutathione and generated reactive oxygen species (radicals) inside A549 cancer cells. These reactive oxygen species were shown to be involved in cell death. These iodide complexes were also found to be cytotoxic towards non-cancerous WI38 human lung cells (IC₅₀ 1-6 μM) and attempts were made to target one complex specifically to cancer cells, through conjugation to transferrin.

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28

Shephard, Douglas Stuart. "Some cluster chemistry of ruthenium". Thesis, University of Edinburgh, 1996. http://hdl.handle.net/1842/14406.

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This thesis describes research directed towards the synthesis, full chemical, spectroscopic and structural characterisation, and reactivity in selected cases of some ruthenium carbonyl clusters containing both π-donor and σ-donor ligands. Cluster nuclearities range between three and six metal atoms and are shown to display a variety of core geometries. Discussions centred on C-H and C-C activation, redox behaviour., magnetic susceptibility, solid state chemistry, mechanism and supramolecular chemistry are all presented. Chapter one contains some highlights of modern cluster chemistry and pays particular attention to redox, magnetic and C-H activation properties of clusters. The area of materials science is also touched upon in conjunction with the potential input from the cluster chemist. Chapter two describes the synthesis and characterisations of a range of compounds wherein a cluster moiety is bound to an extended polycyclic hydrocarbon framework, with a view to their incorporation into organometallic materials. Chapter three introduces the 'pseudo' arene fulvene in respect to its bonding interactions with clusters. A wide variety of compounds are presented isolated from substitution reactions with the parent cluster carbonyls. Chapter four introduces the concept of linking redox active clusters to a second redox active centre. The redox active centres chosen are based on ferrocene and cobaltocene and linked to the clusters by phosphine groups. Novel magnetic behaviour and reactivity has been observed in these systems. Chapter five contains a varied set of compounds which are essentially collections of clusters bound to more exotic π-donor ligands. This work focuses on the use of functional groups such as carboxylates and macrocycles for polymer precursors or host compounds or to give chirality to the cluster bound fragment. Chapter six presents the experimental details of the various methods of synthesis and characterisation used. It also contains spectroscopic and solid state data of the compounds.

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29

Ward, Donald William Bercaw John E. "Stereoselective ruthenium-catalyzed olefin metathesis /". Diss., Pasadena, Calif. : California Institute of Technology, 2004. http://resolver.caltech.edu/CaltechETD:etd-07152003-183214.

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30

Park, Sunghan. "Planar chiral arene ruthenium complexes". Thesis, Canberra, ACT : The Australian National University, 1993. http://hdl.handle.net/1885/140056.

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31

Pelzer, Katrin. "Ruthenium nanoparticles synthesis, characterisation and organisation in aluminia membranes and mesoporous materials ; applications in catalysis /". [S.l. : s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=971183279.

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32

Van, Aswegen Werner. "The kinetics and associated reactions of ruthenium(VIII)". Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/1130.

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This study investigated the reduction reaction of ruthenium tetroxide by various aliphatic alcohols in acidic medium. UV-Vis spectroscopy still plays an essential role in the analysis and study of volatile ruthenium tetroxide and was used in this study to collect kinetic data. This data was analyzed using graphical and computational methods, such as Mauser diagrams and kinetic simulation software. From the results obtained it is proposed that the reaction occurs by the following two-step reaction model: Ru(VIII) k1 Ru(VI) Ru(VI) k2 k-2 Ru(III) Molar extinction coefficients and conditional rate constants were calculated using kinetic simulating software and a hydride transfer mechanism was proposed. The temperature dependence of this reduction reaction was also investigated and thermodynamic parameters calculated. Ruthenium concentrations were determined using a method employing UV-Vis spectroscopy. The method proved to be a reliable, sensitive and simple technique.

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33

Venkataraman, Shyam S. Chyan Oliver Ming-Ren. "Electrodeposition of copper on ruthenium oxides and bimetallic corrosion of copper/ruthenium in polyphenolic antioxidants". [Denton, Tex.] : University of North Texas, 2007. http://digital.library.unt.edu/permalink/meta-dc-3908.

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34

Getty, Kendra Joyce. "Ruthenium K-edge X-ray absorption spectroscopy studies of ruthenium complexes relevant to olefin metathesis". Thesis, University of British Columbia, 2008. http://hdl.handle.net/2429/657.

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Despite previous extensive study of the widely-employed ruthenium-catalysed olefin metathesis reaction, the finer mechanistic details have not been elucidated. An area that is noticeably lacking is spectroscopic exploration of the relevant complexes. In this work, organometallic ruthenium complexes of importance to olefin metathesis have been investigated using Ru K-edge X-ray absorption spectroscopy. The lowest energy feature in the Ru K-edge spectrum has been unambiguously assigned as due to Ru 4d←1s transitions. These electric-dipole-forbidden transitions are extremely sensitive to geometry. For centrosymmetric complexes, the pre-edge feature has very low intensity because it is limited by the weak electric quadrupole mechanism. By contrast, non-centrosymmetric complexes exhibit a substantial increase in pre-edge intensity because Ru 5p-4d mixing introduces electric-dipole-allowed character to the Ru 4d←1s transitions. The energy of the edge feature in the Ru K-edge spectrum corresponds to ionisation of 1s electrons and is a good indicator of the charge on the metal centre. Unexpectedly, we found that the first-generation (L = PCy₃) Grubbs precatalyst (1) has a higher 1s ionisation energy than the second-generation (L = H₂IMes) complex (2). This effect provides a compelling rationale for the unexplained differences in phosphine dissociation kinetics for complexes 1 and 2: the phosphine dissociation rate of 2 is slower than 1 because the metal centre is more electron-deficient in 2. Density functional theory calculations confirm the charge differences and offer some insight into the nature of bonding in these complexes, particularly with regard to the N-heterocyclic carbene and trialkylphosphine ligands. On the basis of these results, we propose that, for this system, the NHC ligand is a weaker σ-charge donor than the phosphine ligand, and that the NHC accepts significant π-electron density from the metal; both interactions function to reduce the electron density on the ruthenium centre. An ultimate goal is to investigate reactive species in the olefin metathesis mechanism; accordingly, we have made considerable progress toward collecting XAS data for a metallacyclobutane species, and we are pursuing methods to trap the four-coordinate intermediate in the metathesis cycle.

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35

Venkataraman, Shyam S. "Electrodeposition of Copper on Ruthenium Oxides and Bimetallic Corrosion of Copper/Ruthenium in Polyphenolic Antioxidants". Thesis, University of North Texas, 2007. https://digital.library.unt.edu/ark:/67531/metadc3908/.

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Copper (Cu) electrodeposition on ruthenium (Ru) oxides was studied due to important implications in semiconductor industry. Ruthenium, proposed as the copper diffusion barrier/liner material, has higher oxygen affinity to form different oxides. Three different oxides (the native oxide, reversible oxide, and irreversible oxide) were studied. Native oxide can be formed on exposing Ru in atmosphere. The reversible and irreversible oxides can be formed by applying electrochemical potential. Investigation of Cu under potential deposition on these oxides indicates the similarity between native and reversible oxides by its nature of inhibiting Cu deposition. Irreversible oxide formed on Ru surface is rather conductive and interfacial binding between Cu and Ru is greatly enhanced. After deposition, bimetallic corrosion of Cu/Ru in different polyphenols was studied. Polyphenols are widely used as antioxidants in post chemical mechanical planarization (CMP). For this purpose, different trihydroxyl substituted benzenes were used as antioxidants. Ru, with its noble nature enhances bimetallic corrosion of Cu. Gallic acid (3,4,5 - trihydroxybenzoic acid) was chosen as model compound. A mechanism has been proposed and validity of the mechanism was checked with other antioxidants. Results show that understanding the chemical structure of antioxidants is necessary during its course of reaction with Cu.

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36

Zhang, Yibin. "Study of Ruthenium and Ruthenium Oxide's Electrochemical Properties and Application as a Copper Diffusion Barrier". Thesis, University of North Texas, 2005. https://digital.library.unt.edu/ark:/67531/metadc4825/.

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As a very promising material of copper diffusion barrier for next generation microelectronics, Ru has already obtained a considerable attention recently. In this dissertation, we investigated ruthenium and ruthenium oxide electrochemical properties and the application as a copper diffusion barrier. Cu under potential deposition (UPD) on the RuOx formed electrochemically was first observed. Strong binding interaction, manifesting by the observed Cu UPD process, exists between Cu and Ru as well as its conductive ruthenium oxide. Since UPD can be conformally formed on the electrode surface, which enable Ru and RuOx has a potential application in the next generation anode. The [Cl-] and pH dependent experiment were conducted, both of them will affect UPD Cu on Ru oxide. We also found the Cu deposition is thermodynamically favored on RuOx formed electrochemically. We have studied the Ru thin film (5nm) as a copper diffusion barrier. It can successfully block Cu diffusion annealed at 300 oC for 10min under vacuum, and fail at 450 oC. We think the silicidation process at the interface between Ru and Si. PVD Cu/Ru/Si and ECP Cu/Ru/Si were compared each other during copper diffusion study. It was observed that ECP Cu is easy to diffuse through Ru barrier. The function of RuOx in diffusion study on Cu/Ru/Si stack was discussed. In pH 5 Cu2+ solution, Ru and Pt electrochemical behavior were investigated. A sharp difference was observed compared to low pH value. The mechanism in pH 5 Cu2+ solution was interpreted. An interesting compound (posnjakite) was obtained during the electrochemical process. An appropriate formation mechanism was proposed. Also Cu2O was formed in the process. We found oxygen reduction reaction is a key factor to cause this phenomenon.

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37

Zheng, Sipeng. "The reactions of ruthenium (ii) polypyridyl complexes". Thesis, Nelson Mandela Metropolitan University, 2009. http://hdl.handle.net/10948/1089.

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Ruthenium (II) polypyridine complexes in general have been extensively studied because of their unique redox and photochemical properties. A typical example of such complexes is tris(2,2’-bipyridyl) ruthenium (II). In this study, this complex was synthesized and then characterized using electronic spectroscopy and cyclic voltammetry. It was also shown that the ruthenium concentration could be accurately determined using ICP-MS. It was found that the complex is very stable in various chemical environments. It was observed from spectrophotometric investigations that persulphate and lead dioxide easily oxidize Ru(bpy)3 2+ to Ru(bpy)3 3+ in the presence of heat and H2SO4, respectively. It was also observed that the oxidation between Ru(bpy)3 2+ and cerium (IV) occurred at approximately 3:2 [Ce(IV)]/[Ru(II)] mole ratio. The resultant Ru(bpy)3 3+ solution was unstable in the presence of light and recovery of Ru(bpy)3 2+ occurred gradually. The regeneration of Ru(bpy)3 2+ from Ru(bpy)3 3+ was found to be a multistep process, which appears to involve the formation of an intermediate species. The following reaction model was found to best explain the kinetic data obtained: Ru(bpy)3 2+ + Ce(IV) → Ru(bpy)3 3+ Ru(bpy)3 3+ → Ru(bpy)3 2+ Ru(bpy)3 3+ → Ru* intermediate Ru* intermediate → Ru(bpy)3 2+ Theoretical rate constants were also calculated for the same process under the experimental conditions. The comparison between the experimental and theoretical results gave good agreement. In addition, the factors that influence the rate of the regeneration of Ru(bpy)3 2+ from Ru(bpy)3 3+ were also discussed.

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38

Wong, Chun-yuen. "Ruthenium-carbon bonding interaction synthesis and spectroscopic studies of ruthenium-acetylide, -carbene, -vinylidene and -allenylidene complexes". Click to view the E-thesis via HKUTO, 2004. http://sunzi.lib.hku.hk/hkuto/record/B31040858.

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39

Williams, Joseph Ephraim. "Ruthenium incorporation into molecules and materials New catalysts and strategies to prepare stable ruthenium-capped olefins /". Related electronic resource: Current Research at SU : database of SU dissertations, recent titles available full text, 2005. http://wwwlib.umi.com/cr/syr/main.

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40

Wong, Chun-yuen y 黃駿弦. "Ruthenium-carbon bonding interaction synthesis and spectroscopic studies of ruthenium-acetylide, -carbene, -vinylidene and -allenylidene complexes". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2004. http://hub.hku.hk/bib/B31040858.

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41

Sanchez, Richard P. Jr. "Cationic Ruthenium Catalysts for Olefin Hydrovinylation". [College Station, Tex. : Texas A&M University, 2009. http://hdl.handle.net/1969.1/ETD-TAMU-2009-08-2929.

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42

Santoro, Francesco. "Ruthenium/PNNP-catalyzed asymmetric Michael addition /". Zürich : ETH, 2007. http://e-collection.ethbib.ethz.ch/show?type=diss&nr=17024.

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43

Creus, Casanovas Jordi. "Electrocatalytic water splitting with ruthenium nanoparticles". Doctoral thesis, Universitat Autònoma de Barcelona, 2018. http://hdl.handle.net/10803/664045.

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L’estudi de sistemes basats en nanopartícules per a la catàlisi de les reaccions de reducció de protons a hidrogen (HER) i oxidació d’aigua a oxigen (OER) permet el disseny i desenvolupament de noves espècies catalítiques de manera racional, les quals poden millorar l’eficiència de la reacció de dissociació de l’aigua o “water splitting” (WS) per l’obtenció de H2, fent d’aquest procés una alternativa viable als combustibles fòssils. D’entre els metalls més utilitzats, el Pt i l’Ir són els que han donat millors resultats d’activitat i estabilitat per la HER i l’OER, respectivament. En aquest sentit, bona part d’investigació en el camp és dedicada a estudiar i entendre les interaccions que tenen part entre les diferents espècies durant la catàlisi, per poder transferir aquest coneixement a altres espècies basades en metalls més barats. El Ruteni podria ser una alternativa als metalls Pt/Ir, tenint en compte la seva versatilitat i la possibilitat que ofereix a ser estudiat mitjançant un ampli ventall de tècniques analítiques com a resultat de les seves propietats. L’objectiu d’aquesta tesis doctoral és el de desenvolupar nano-materials basats en Ru com a catalitzadors per a les reaccions de HER i OER, i estudiar-ne les característiques que indueixen una certa activitat catalítica. L’ús del mètode organometàl·lic com a procediment de síntesis de nanopartícules permet l’obtenció d’aquestes amb un control en les propietats que les defineixen com ara el diàmetre, l’entorn superficial o la dispersió. El mètode organometàl·lic permet l’addició d’agents coordinants a la mescla de reacció, els quals aturen la nucleació termodinàmica per formar un material “bulk” i estabilitzen la formació de partícules de mida nanomètrica. Aquestes espècies poden influenciar no només en la síntesi dels materials, sinó també a la reactivitat de les NPs, un efecte molt important pels processos catalítics en què poden estar involucrades. A més a més de la formació de partícules col·loïdals, una altra possibilitat que ofereix l’aproximació organometàl·lica és la síntesis de NPs a la superfície d’un suport com ara nanotubs de carboni, fibres, òxids metàl·lics, MOFs, etc. Aquest mètode va ser desenvolupat per primera vegada en el grup de recerca de la Dr. Philippot tres dècades enrere i actualment és àmpliament utilitzat per un número de grups d’investigació elevat. En resum, en aquesta memòria es descriu la síntesi de RuNPs per la seva avaluació com a catalitzadors per la HER i l’OER, amb l’objectiu d’entendre quines propietats de les NPs afecten els diferents passos catalítics i així ser capaços de dissenyar nous catalitzadors amb un millor rendiment catalític per la producció d’H2 a partir de l’aigua.
The study of nanoparticulated systems for the hydrogen evolution (HER) and oxygen evolution (OER) reactions allows to rationally design new catalysts that enhance the water splitting process for obtaining H2, and thus making it a suitable alternative to fossil fuels as energy carriers. Nowadays Pt and Ir are the leading metals in HE and OE catalysts, respectively, but a huge effort is being devoted to understand the mechanistic pathways that rule both semi-reactions in order to transfer the knowledge to other metals which can be more abundant and thus cheaper. Ru appears as a feasible alternative to deeply explore the reaction steps involved in the process, because it is a highly-versatile metal which shows similar activities than Pt/Ir and which can be studied by a wide range of analytical techniques as a result of its properties. In addition, Ru is four times cheaper than the state-of-the-art Pt. This PhD work aims to develop Ru-based nanocatalysts for both HER and OER, and study the characteristics that induce a specific catalytic response. The use of the organometallic approach as synthetic methodology allows to finely control the properties of the NPs, e.g. size, surface environment, dispersion, etc. In this synthetic procedure, organic ligands can be added as stabilizing agents to halt the nucleation of metal atoms leading to the formation of the nanosized systems. These ligands can alter the chemical properties of the surface of the nanoparticles, a key feature in the catalytic processes. This methodology allows as well the preparation of metal nanoparticles onto the surface of solid supports, e.g. carbon nano-tubes, fibers, metal oxides, MOFs, etc. The organometallic approach was first developed in our group around three decades ago, and today its wide use by the global scientific community has brought a large knowledge on different nanometric systems. The development of precisely controlled nanocatalysts for their application in challenging catalysis like the production of H2 by water-splitting lies among our research interests. To sum up, the synthesis of Ru-NPs and their evaluation as catalysts for the HER and OER are described, aiming to understand the factors ruling the catalytic steps on the surface of the particles, to be able to rationally design new catalysts that make the water splitting process efficient enough to replace fossil fuels by H2.

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44

Henning, Frauke. "Enantioselektive Transferhydrierung mit Ruthenium(II)-Komplexen". [S.l. : s.n.], 2003. http://deposit.ddb.de/cgi-bin/dokserv?idn=969398867.

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45

Malmgren, Christine. "Nanoscaled Structures in Ruthenium Dioxide Coatings". Licentiate thesis, Mid Sweden University, Department of Natural Sciences, Engineering and Mathematics, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:miun:diva-8728.

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An essential ingredient in the generation of environmentally compatible pulp bleaching chemicals is sodium chlorate. Chlorate is produced in electrochemical cells, where the electrodes are the key components. In Sweden the so-called DSA !R electrodes with catalytic coatings have been produced for more than 35 years. The production of chlorate uses a large amount of electric energy, and a decrease of just five percent of this consumption would, globally, decrease the consumption of electrical energy corresponding to half a nuclear power reactor. The aim of this project is to improve the electrode design on the nanoscale to decrease the energy consumption. The success of the DSA!R depends on the large catalytic area of the coating, however, little is known about the actual structure at the nanometer level. To increase the understanding of the nanostructure of these coatings, we used a number of methods, including atomic force microscopy, transmission electron microscopy, X-ray diffraction, porosimetry, and voltammetric charge. We found that the entire coating is built up of loosely packed rutile mono-crystalline 20 − 30 nm sized grains. The small grain sizes give a the large area, and consequently, lower cell-voltage and reduced energy consumption. A method to control the grain size would thus be a way to control the electrode efficiency. To alter the catalytically active area, we made changes in the coating process parameters. We found a dependency of the crystal-grain sizes on the choice of ruthenium precursor and processing temperature. The use of ruthenium nitrosyl nitrate resulted in smaller grains than ruthenium chloride and lowering the temperature tended to favour smaller grains. A more radical way would be to create a totally different type of electrode, manufactured in another way than using the 1965 DSA !R recipe. Such new types of electrodes based on, for example, nanowires or nanoimprint lithography, are discussed as future directions.

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46

Farrington, Edward. "Ruthenium-catalysed carbon-carbon bond formation". Thesis, University of Oxford, 2001. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.393397.

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47

Blank, Jan Hendrik. "Carbon monoxide hydrogenation using ruthenium catalysts". Thesis, University of St Andrews, 2012. http://hdl.handle.net/10023/3470.

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48

Almodares, Zahra. "Ruthenium compounds as anti-tumour agents". Thesis, University of Leeds, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.531426.

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49

Davison, Thomas William. "Ruthenium complexes of new heterocyclic ligands". Thesis, University of Canterbury. Chemistry, 2014. http://hdl.handle.net/10092/9370.

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The coordination chemistry of eight chelating heterocyclic ligands is described. These ligands all contain heterocyclic ring systems with bridgehead nitrogens, and have received little attention in the literature. The ring systems examined are, specifically, imidazo[1,2-a]pyridine, imidazo[1,5-a]pyridine and triazolo[1,5-a]pyridine. The coordination complexes synthesised are mononuclear ruthenium(II) complexes, of the type [Ru(bpy)2(L)]2+. Complexes have been examined by a combination of 1H and 13C NMR, UV-visible spectroscopy, cyclic voltammetry, and X-ray crystallography, in order to study their metal-ligand interactions. A total of six complexes were analysed by single crystal X-ray diffractometry, and the resulting structures are described herein. In general, the inclusion of these ligands had the effect of raising the HOMO and lowering the LUMO, relative to the [Ru(bpy)3]2+ complex. As a result, the complexes were easier to oxidise, harder to reduce, and absorb visible light at longer wavelengths.

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50

Liang, Jianglin y 梁江林. "Ruthenium-catalyzed carbon-nitrogen bond formations". Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2003. http://hub.hku.hk/bib/B31245729.

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