Teses / dissertações sobre o tema "Ruthenium-based catalysts"
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Robinson, Alan. "Novel catalysts and additives for ruthenium-based metathesis systems". Thesis, University of Bristol, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.508098.
Texto completo da fonteMOTOKI, YOSHIDA. "Synthesis of Ruthenium-based Water Oxidation Catalysts and Mechanistic Study". Thesis, KTH, Skolan för kemivetenskap (CHE), 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-173843.
Texto completo da fonteUrbina-Blanco, César A. "Design and synthesis of ruthenium indenylidene-based catalysts for olefin metathesis". Thesis, University of St Andrews, 2013. http://hdl.handle.net/10023/3737.
Texto completo da fonteGowda, Anitha Shankaralinge. "HYDROGENATION AND HYDROGENOLYSIS OF FURAN DERIVATIVES USING BIPYRIDINE-BASED ELECTROPHILIC RUTHENIUM(II) CATALYSTS". UKnowledge, 2013. http://uknowledge.uky.edu/chemistry_etds/29.
Texto completo da fonteBashal, Ali Habib. "Aqueous phase hydrogenation of succinic acid using mono-and bi-metallic ruthenium-based catalysts". Thesis, University of Liverpool, 2018. http://livrepository.liverpool.ac.uk/3021601/.
Texto completo da fonteMorgan, John Philip Stoltz Brian M. Grubbs Robert H. "Ruthenium-based olefin metathesis catalysts coordinated with n-heterocyclic carbene ligands : synthesis and applications /". Diss., Pasadena, Calif. : California Institute of Technology, 2003. http://resolver.caltech.edu/CaltechETD:etd-10222002-204928.
Texto completo da fonteFraser, Ian. "The feasibility of high synthesis gas conversion over ruthenium promoted iron-based Fischer Tropsch catalyst". Thesis, Cape Peninsula University of Technology, 2017. http://hdl.handle.net/20.500.11838/2588.
Texto completo da fonteOne of the very promising synthetic fuel production strategies is the Fischer-Tropsch process, founded on the Fischer-Tropsch Synthesis, which owes its discovery to the namesake researchers Franz Fischer and Hans Tropsch. The Fischer-Tropsch Synthesis (FTS) converts via complex polymerisation reaction a mixture of CO and H2 over transition metal catalysts to a complex mixture of hydrocarbons and oxygen containing compounds with water as major by-product. The mixture of CO and H2 (termed syngas) may be obtained by partial oxidation of carbon containing base feedstocks such as coal, biomass or natural gas via gasification or reforming. The Fischer-Tropsch (FT) process thus presents the opportunity to convert carbon containing feedstocks to liquid fuels, chemicals or hydrocarbon waxes, which makes, for instance, the monetisation of stranded gas or associated gas a possibility. The FT-process is typically carried out in two modes of operation: low temperature Fischer-Tropsch (LTFT) and high temperature Fischer-Tropsch (HTFT). LTFT is normally operated at temperatures of 200 – 250 °C and pressures of 10 – 45 bar to target production of high molecular weight hydrocarbons, while HTFT is operated at 300 – 350 °C and 25 bar to target gasoline production. The catalytically active metals currently used commercially are iron and cobalt, since product selectivity over nickel is almost exclusively to methane and ruthenium is highly expensive in addition to requiring very high pressures to perform optimally. Fe is much cheaper, but tends to deactivate more rapidly than Co due to oxidation in the presence of high H2O partial pressures. One of the major drawbacks to using Fe as FT catalyst is the requirement of lower per pass conversion which necessitates tail gas recycle to extend catalyst life and attain acceptable overall conversions. A more active or similarly active but more stable Fe-catalyst would thus be advantageous. For this reason promotion of a self-prepared typical LTFT Fe-catalyst with Ru was investigated. A precipitated K-promoted Fe-catalyst was prepared by combination of co-precipitation and incipient wetness impregnation and a ruthenium containing catalyst prepared from this by impregnation with Ru3(CO)12. The catalysts, which had a target composition of 100 Fe/30 Al2O3/5 K and 100 Fe/30 Al2O3/5 K/3 Ru, were characterised using XRD, SEMEDX, ICP-OES, TPR and BET N2-physisorption, before testing at LTFT conditions of 250 °C and 20 bar in a continuously stirred slurry phase reactor.
Zhang, Hui-Jun. "Novel syntheses from building blocks based on 1,3-butadienyl skeleton and new polysubstitued ruthenium based catalysts for regioselective allylation". Rennes 1, 2010. http://www.theses.fr/2010REN1S011.
Texto completo da fonteUn objectif de cette thèse était la préparation de nouveaux fragments organique à partir du squelette butadiényle et leurs applications en synthèse organique. Des 1,1,4,4-tétrahalo-1,3-butadiènes ont été préparés de façon stéréosélective. La réaction de ces butadiènes avec le butyllithium et leur couplage de Suzuki avec des acides arylboroniques constituent des transformations nouvelles et originales. De nouveaux gem-diboryldiènes, également d���excellents agents de couplage de Suzuki, ont été obtenus à partir des gem-dihalodiènes correspondants. Le traitement avec LiAlH₄ de 1,4-dicyano-1,4-bis(triméthylsilyl)-1,3-diènes a conduit à une nouvelle réaction de cyclisation induite par des hydrures pour former des cyclopentadiènes multi-fonctionnalisés avec de très bons rendements. Dans un deuxième objectif, une série de complexes inédits du ruthénium porteurs de nouveaux ligands Cp et N-O chelatants ont été conçus et préparés avec l’objectif d’obtenir de bonnes propriétés catalytiques en allylation de nucléophiles. Ces complexes ont été utilisés comme catalyseurs d’allylation et ont conduit pour la première fois à d’excellentes régiosélectivités en faveur des produits branchés à partir de substrats allyliques purement aliphatiques et à la préparation de dérivés vinylsilanes fonctionnels
Delgado, Jaime Mario Ulises. "Electronic structure studies of ruthenium-based catalysts for olefin metathesis : an x-ray absoprtion spectroscopy perspective". Thesis, University of British Columbia, 2009. http://hdl.handle.net/2429/17434.
Texto completo da fonteBernardi, Andrea. "Synthesis, characterization and catalytic performances of ruthenium-based catalysts for the acceptorless dehydrogenative coupling of butanol". Master's thesis, Alma Mater Studiorum - Università di Bologna, 2015. http://amslaurea.unibo.it/8521/.
Texto completo da fonteSchmid, Thibault E. "Synergism between N-heterocyclic carbene and phosphorus-based ligands in ruthenium and palladium catalytic systems". Thesis, University of St Andrews, 2012. http://hdl.handle.net/10023/3452.
Texto completo da fonteBayrakceken, Ayse. "Platinum And Platinum-ruthenium Based Catalysts On Various Carbon Supports Prepared By Different Methods For Pem Fuel Cell Applications". Phd thesis, METU, 2008. http://etd.lib.metu.edu.tr/upload/12609448/index.pdf.
Texto completo da fontePlatinum/MWCNT>
PlatinumBP2000. By means of the oxygen reduction reaction (ORR), the number of electrons transferred per oxygen molecule was calculated as 3.5, 3.6 and 3.7 for Platinum/BP2000, Platinum/VXR and Platinum/MWCNT, respectively. The microwave irradiation was used to prepare platinum on VX, Regal and BP2000 and platinum-ruthenium on VX. The effects of microwave duration, base concentration, carbon support used and surfactant/precursor ratios were investigated. The particle sizes of the catalysts were ranging between 2-6 nm. The prepared catalysts were characterized by XRD, XPS, and then PEMFC tests were performed. The performance was ordered as Platinum/VX>
Platinum/Regal>
Platinum/BP2000. The power losses arising from carbon dioxide in hydrogen feed were decreased by using prepared platinum-ruthenium based catalysts.
Kleinschmidt, Denise Verfasser], Andrij [Akademischer Betreuer] Pich e Sonja [Akademischer Betreuer] [Herres-Pawlis. "Switchable colloidal L-proline and ruthenium nanoparticle catalysts based on responsive microgels / Denise Kleinschmidt ; Andrij Pich, Sonja Herres-Pawlis". Aachen : Universitätsbibliothek der RWTH Aachen, 2021. http://d-nb.info/1239116845/34.
Texto completo da fonteSavka, Roman [Verfasser], Herbert [Akademischer Betreuer] Plenio, Michael [Akademischer Betreuer] Reggelin, Jörg J. [Akademischer Betreuer] Schneider e Rolf [Akademischer Betreuer] Schäfer. "Synthesis and Application of New Ruthenium-Based Olefin Metathesis Catalysts / Roman Savka. Betreuer: Herbert Plenio ; Michael Reggelin ; Jörg J. Schneider ; Rolf Schäfer". Darmstadt : Universitäts- und Landesbibliothek Darmstadt, 2014. http://d-nb.info/1110792301/34.
Texto completo da fonteTalcik, Jakub. "Conception de catalyseurs chiraux de ruthénium à base de carbènes alkyles amino cycliques (CAACs) pour la métathèse asymétrique des oléfines". Electronic Thesis or Diss., Université de Rennes (2023-....), 2024. http://www.theses.fr/2024URENC001.
Texto completo da fonteOlefin metathesis is an important reaction of green chemistry for the formation of new carbon-carbon double bonds. Allowing a better atom economy and shortening synthetic pathways, this technology offers many advantages for the production of highly valuable molecules. Thus, numerous ruthenium-based complexes have been developed since the 1990s aiming to extend the field of application of metathesis. While major advances were reached in terms of activity and stability of these precatalysts, controlling the selectivity of the reaction during the formation of stereogenic centers is still a major challenge.Hence, in this PhD thesis, two new families of chiral Cyclic alkylaminocarbenes (CAAC)-based ruthenium complexes were developed. Complexes containing CAACs that combined both centered and axial chirality enabled to achieve excellent enantioselectivities up to 99% ee in Asymmetric ring-opening cross metathesis (AROCM). Blechert type CAAC-Ru complexes reached remarkable activity at loadings below 0.05 mol% with very high enantioselectivities (95% ee). Finally, a novel class of CAAC family ligands carrying a barrelene scaffold (CABCs) was studied and the associated Ru complexes were evaluated across various metathesis reactions
エカ, プトラ アンギ, e Anggi Eka Putra. "Studies on ruthenium-catalyzed "Borrowing Hydrogen"-based organic reactions". Thesis, https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB12905970/?lang=0, 2014. https://doors.doshisha.ac.jp/opac/opac_link/bibid/BB12905970/?lang=0.
Texto completo da fonteSeveral novel ruthenium-catalyzed "borrowing hydrogen"-based organic reaction has been developed. For very first time optically active β-amino alcohols can be sinthesized directy by reaction of 1,2-diol and coressponding amine under Ru/JOSIPHOS catalysis in up to 99% yield and 77% ee. Since this reaction is very new, intensive investigation of the reaction mechanism was also carried out. Meanwhile, combination of RuCl2(PPh3)3/DPEphos/K3PO4 was found to be effective catalyst for alkylation of indole with alcohol as an alkylating reagent. This catalysis was highly reactive to give the corresponding alkylated indole in excellent yield for almost all types of indoles and alcohols substrates.
博士(工学)
Doctor of Philosophy in Engineering
同志社大学
Doshisha University
Nieczypor, Piotr. "Immobilisation of Ru-based metathesis catalysts and related aspects of olefin metathesis". [S.l. : Amsterdam : s.n.] ; Universiteit van Amsterdam [Host], 2004. http://dare.uva.nl/document/74260.
Texto completo da fonteXu, Chaofan. "New Ru-Based Catalysts and Strategies for Kinetically Controlled Stereoselective Olefin Metathesis:". Thesis, Boston College, 2020. http://hdl.handle.net/2345/bc-ir:109015.
Texto completo da fonteChapter 1. In Situ Methylene Capping: A Key Strategy in Catalytic Stereoretentive Olefin MetathesisA general approach for in situ methylene capping that significantly expands the scope of catalyst-controlled stereoselective olefin metathesis is presented. By incorporation of stereodefined 2-butene as the capping reagent, the catechothiolate Ru complex is enabled to catalyze olefin metathesis reactions of terminal alkenes. Substrates bearing a carboxylic acid, an aldehyde, an aryl substituent, an α substituent were thus converted to the desired products in 47–88% yield and 90:10–98:2 Z:E selectivity. The capping strategy was also applied in ring-closing metathesis reactions leading to 14- to 21-membered macrocyclic alkenes (96:4–98:2 Z:E). The utility of this method was highlighted through synthesis of a platelet aggregate inhibitor and two members of the prostaglandin family compounds by cross-metathesis reaction, as well as a strained 14-membered ring stapled peptide by macrocyclic ring-closing metathesis. Examples of the corresponding E-selective cross-processes are provided as well. Chapter 2. Synthesis of Z- or E-Trisubstituted Allylic Alcohols and Ethers by Kinetically Controlled Catalytic Cross-MetathesisKinetically controlled Ru-catalyzed cross-metathesis reactions that generate Z- or E-trisubstituted alkenes are discussed. Reactions were catalyzed by catechothiolate Ru complex to generate trisubstituted allylic alcohols and ethers in up to 81% yield and >98% stereoisomeric purity. The approach is applicable to synthesis of products containing an alcohol, an aldehyde, a carboxylic acid or an alkenyl substituent. Mechanistic models that account for the observed trends in efficiency and stereoselectivity will be provided. Chapter 3. A New Ru-Based Catechothiolate Complex Bearing an Unsaturated NHC Ligand for Synthesis of Z-α,β-Unsaturated Carbonyl Compounds by Cross Metathesis Design and development of a new Ru catechothiolate complex that may be used to promote Z-selective cross-metathesis transformations that afford Z-α,β-unsaturated esters, acids, and amides (including Weinweb amides) are discussed. Comparison between Ru catechothiolate complexes with an unsaturated NHC and a saturated NHC ligand will be provided. Utility of the approach is demonstrated by an eight-step synthesis (15% overall yield) of an intermediate for synthesis of stagonolide E, and a five-step synthesis of a precursor to dihydrocompactin
Thesis (PhD) — Boston College, 2020
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Margue, Robert Germain. "Mechanistic investigations of enyne ring-closing metathesis reactions catalysed by ruthenium based systems". Thesis, University of Bristol, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.431634.
Texto completo da fonteCalcagno, Francesco. "Theoretical and experimental investigations on homologation of ethanol to butanol using a ruthenium-based catalyst". Master's thesis, Alma Mater Studiorum - Università di Bologna, 2021. http://amslaurea.unibo.it/23597/.
Texto completo da fonteZhugralin, Adil R. "Combined Theoretical and Experimental Investigation of N-Heterocyclic Carbenes as Lewis Base Catalysts and as Ancillary Ligands in Ru-Catalyzed Olefin Metathesis. Mechanistic Investigation of Fluxional Behavior of Ru-Based Olefin Metathesis Catalysts". Thesis, Boston College, 2011. http://hdl.handle.net/2345/2973.
Texto completo da fonteChapter 1. Through the use of quantum theory of atoms in molecules (QTAIM) the similarities and differences between transition metal complexes ligated by phosphines and N-heterocyclic carbenes (NHC) were elucidated. Among the key findings, the phosphines were identified as stronger charge donors than NHCs; however, the latter class of ligands exhibits a weaker p-accepting character than the former. Furthermore, Tolman electronic parameter (TEP) was determined to be an inadequate gauge for the total electron donating ability of phosphines and NHCs; rather TEP can serve as a measurement of population of dp set of orbitals of a metal center in question. Computational and experimental studies of the mechanism of NHC-catalyzed boron and silicon addition to a,ß-unsaturated carbonyls reactions were carried out. Through the use of radical traps the mechanisms involving homolytic cleavage of B-B or B-Si bonds were ruled out. Computational (DFT) studies of the mechanism identified two pathways: (1) direct activation of diboron or borosilyl reagents through coordination of NHC to the B atom, (2) net oxidative addition of the diboron or borosilyl reagents to the carbon (II) of the NHC. The insights gained from the aforementioned studies were employed to rationalize the observed lack of reactivity of NHC-activated diboron complexes in the presence of aldehydes. Chapter 2. New C(1)-symmetric chiral monodentate N-heterocyclic carbenes were prepared, and corresponding chiral Ru-carbene complexes were synthesized. These complexes were employed to gain empirical understanding of factors that govern stereoselectivity in Ru-catalyzed enantioselective olefin ring-closing metathesis. The data thus obtained was employed to infer that syn-to-NHC reaction pathways are competitive and non-selective. One plausible mechanism, through which syn-to-NHC pathways can be accessed, involves Berry pseudorotations. Through the use of stereogenic-at-Ru complexes diastereomeric Ru-carbenes were isolated (silica gel chromatography) and spectroscopically characterized in solution phase. The diastereomeric Ru-carbenes were found to undergo non-metathesis stereomutations at Ru center, thereby providing additional support for the above hypothesis regarding accessibility of syn-to-NHC olefin metathesis pathways. Non-metathesis stereomutation at Ru was found to be accelerated in the presence of protic additives, suggesting the plausibility of hydrogen bonding between the acidic proton and the X-type ligands on Ru. Occurrence of hydrogen bonding was corroborated through the use of chiral allylic alcohols in Ru-catalyzed diastereoselective ring-opening/cross metathesis, which was developed into a versatile method for highly diastereoselective functionalization of terminal olefins
Thesis (PhD) — Boston College, 2011
Submitted to: Boston College. Graduate School of Arts and Sciences
Discipline: Chemistry
Peiris, W. Pubudu M. "New Generation of Electrochemical Sensors for Nitric Oxide: Ruthenium/Carbon-Based Nanostructures and Colloids as Electrocatalytic Platforms". Cleveland State University / OhioLINK, 2009. http://rave.ohiolink.edu/etdc/view?acc_num=csu1283257971.
Texto completo da fonteWojciechowska, Joanna. "Ru/TiO2-based catalysts for the hydrogenation of levulinic acid using formic acid as internal hydrogen source". Thesis, Strasbourg, 2018. http://www.theses.fr/2018STRAF061/document.
Texto completo da fonteActive and selective Ru catalysts based on TiO2 supports have been developed for the combined hydrogenation of levulinic acid to γ-valerolactone with internal hydrogen supply via in-situ formic acid decomposition. A controlled modification of the TiO2 support by Ca2+ improved the catalytic performance in the one-pot hydrogenation, as a result of enhanced performances in both the formic acid dehydrogenation and the levulinic acid hydrogenation. The improved performances were associated to stronger Ru/support interactions with weaker CO adsorption, as well as to an increased support basicity. The performances were further exalted thanks to a one-step solar light photon-assisted synthesis method used as sustainable alternative to classical wet impregnation. It enabled the uniform dispersion of sub-nanometric metallic Ru particles with narrow distribution and fine size monitoring, and a volcano-type profile centered at 1.5 nm was demonstrated between the nanoparticle size and the activity
Tiyash, Bose. "Ruthenium Oxide Based Combined Electrodes as Nitric Oxide (NO) Sensors: Towards Measuring NO in Cystic Fibrosis Cell Line Models". Cleveland State University / OhioLINK, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=csu1557496991784383.
Texto completo da fonteValente, Andreia. "Lanthanide based coordinative chain transfer polymerization for architecture control in (co)polymers and ruthenium catalyzed ring-opening polymerization : two aspects of atom economy in polymerization catalysis". Thesis, Lille 1, 2010. http://www.theses.fr/2010LIL10061.
Texto completo da fonteA newly synthesized Cp*La(BH4)2(THF)2 complex in combination with magnesium or aluminum alkyls was used for the coordinative chain transfer (co)polymerization (CCTP) of styrene and isoprene. Using this concept, we have accomplished the first catalyzed chain growth like reaction of styrene and isoprene, with control of the microstructure. The application of CCTP to statistical copolymerization represents a new and original approach to tune the composition of copolymers. In addition, a mechanistic study of the ring-opening polymerization of ε-caprolactone by [(η5-C5H5)Ru(η6-substituted arene)][PF6] complexes shows that the polymerization proceeds via an activated monomer mechanism by transfer to the alcohol with a change of hapticity of the arene ligand
Nguyen, Thi Quyen. "Développement de photoélectrodes hybrides via l'assemblage d'un photosensibilisateur à base de ruthénium et d'un nanocatalyseur métal-oxyde métallique pour la génération d'O2 solaire". Thesis, Toulouse 3, 2021. http://www.theses.fr/2021TOU30046.
Texto completo da fonteIn this work, different nanostructured catalytic systems have been synthesized by an organometallic approach to produce nanoparticles (NPs) of small size and narrow size distribution, and their catalytic activity in the water oxidation reaction has been evaluated. First Fe NPs stabilized by oleic acid were synthesized that displayed an average size of ca. 10 nm ± 1.1 nm. A gamma-Fe_2O_3 oxide layer ca. 2.6 nm thick has been formed at their surface to obtain Fe@FeOx core-shell structure of ca. 11.5 ± 2.3 nm in diameter. Despite their hydrophobicity, these nanoparticles showed good electrocatalytic activity in alkaline conditions. As the gamma-Fe_2O_3 oxide shell is well adapted to the grafting of phosphonic groups, these Fe@FeOx NPs were grafted with different aminophosphonic acids in order to transfer them into water. Preliminary assessment of their catalytic activity showed improved activity for the NPs functionalized by 3-aminopropylphosphonic acid which opens promising prospects. Subsequently, a Ru-phenanthroline light-harvester with a pendant phosphonate group was synthesized and grafted onto the Fe@FeOx core/shell NPs to afford a novel hybrid photoanode for solar-driven water splitting. Mono- and biphasic processes were investigated to graft the Ru-complex at the surface of the NPs. The monophasic process was found to be more efficient as it provided a higher grafting density at the surface of the NPs (respectively 56 and 9 Ru per nanoparticles for the mono and biphasic processes). Photoelectrochemical measurements showed that the hybrid nanocatalyst comprising the highest Ru content was ca. 9-fold more catalytically active than a simple mixture between a ruthenium polypyridyl photosensitizer bearing no grafting group and the Fe@FeOx nanoparticles, and 40-fold more active than the pristine Fe@FeOx NPs. The performance enhancement could be attributed to a more efficient electron transfer between the ruthenium polypyridyl photosensitizer and the Fe@FeOx water oxidation catalyst thanks to the covalent bonding between these two components. The covalent grafting was found to improve not only the photocatalytic activity but also the stability of the system. Finally, amorphous NiFe NPs (diameter ca. 4 nm) with two different ratios between Ni and Fe (Ni_0.5Fe_0.5 NPs and Ni_0.68Fe_0.32 NPs) were synthesized, oxidized in air and grafted with 3-aminopropylphosphonic acid in order to obtain hydrophilic systems. The electrocatalytic activity of these water-soluble NPs was studied in alkaline solution, in comparison with that of crude NiOx NPs, FeOx NPs, and Ni_0.1Fe_0.9Ox NPs. The water soluble NPs containing 32 % of Fe (Ni_0.68Fe_0.32Ox) showed the highest activity and a good durability in alkaline solution. These characteristics make these amorphous NPs potentially applicable in photoelectrochemical cells for water splitting
Fonseca, Joel David Avelino. "p-cymene based ruthenium complexes as catalysts". Master's thesis, 2011. http://hdl.handle.net/10451/8364.
Texto completo da fontep-Cymene based ruthenium complexes were employed in the alkylation of tbutylamine with phenethyl alcohol by redox neutral alkylation and in the reduction of acetophenone and benzaldehyde by transfer hydrogenation. A range of in situ generated catalysts formed by [RuX2(p-cymene)]2 dimers (X=Cl or I) with dppf, DPEPhos, dippf or P(i- Bu)3 and a range of p-cymene ruthenium monomers, namely [RuCl(dppf)(p-cymene)]SbF6, [RuI(dppf)(p-cymene)]SbF6, [RuCl(dppf)(p-cymene)]BF4, [RuCl(dppf)(p-cymene)]Cl, [RuI(P(n- Bu)3)2(p-cymene)]SbF6, [RuCl(P(i-Bu)3)2(p-cymene)]SbF6, [RuCl2(P(n-Bu)3)2(p-cymene)], [RuCl(P(CH3)3)2(p-cymene)]SbF6 have been employed in these reactions. These monomers have been synthesised and characterized in this project and only [RuCl2(P(n-Bu)3)2(pcymene)] has been already reported in the literature. Results were compared in terms of conversions and the best ones for the redox neutral alkylation were with the in situ generated catalyst formed by [RuI2(p-cymene) and DPEPhos, giving 96% conversion for a catalyst/substrate ratio of 20 and with [RuI(dppf)(pcymene)] SbF6 which gave 85% conversion for a catalyst/substrate ratio of 40. These reactions have been run out in the open air without degassing or inert gas protection throughout which is not the typical approach found in the literature and that can be very appealing in the industrial point of view. The different halides incorporated in these complexes have been proved to have different effects in the catalytic activity, with iodine usually leading to more active catalysts. Some results and experiments that were performed allowed drawing some conclusions about the mechanism. For the reduction of acetophenone and benzaldehyde by transfer hydrogenation it has been demonstrated that the dimers, the dimer-phosphine pairs and the ruthenium monomers mentioned before are not the most suitable pre-catalysts for these reactions. Overall, conversions up to 73% were obtained which lag far behind the 100% reported in the literature for several other complexes. Some conclusions were drawn about the mechanism and two catalytic cycles were proposed. The brand new dimer [Ru2Cl3(DPEPhos)2(CH3CN)2]SbF6 has been serendipitously synthesised and has shown it forms catalytically active species in both the alkylation of tbutylamine and reduction of acetophenone giving moderate conversions.
Neste projecto foram sintetizados complexos de rutenio e p-cimeno que foram posteriormente avaliados do ponto de vista catalitico em reaccoes de transferencia de hidrogenio. Os complexos de rutenio e p-cimento tem demonstrado ser catalisadores/precatalisadores eficientes em varias reaccoes envolvendo compostos organicos e foi inicialmente sugerido para este projecto pela empresa biofarmaceutica Astra Zeneca o estudo da actividade catalitica do dimero [RuCl2(p-cimeno)]2 na presenca das fosfinas DPEPhos, dippf e P(i-Bu)3 em reaccoes de transferencia de hidrogenio. Esta empresa verificou que este dimero e extremamente activo na alquilacao de morfolina com álcool benzilico na presenca das fosfinas referidas (conversoes acima de 97%). No que respeita aos complexos sintetizados, levaram-se a cabo as sinteses dos dimeros de cloro e iodo de formula molecular [RuX2(p-cimeno)]2 em que X = Cl ou I e ainda de monomeros utilizando os dimeros referidos como compostos de partida. A sintese do dimero de bromo foi tambem tentada mas este revelou-se muito dificil de obter e portanto nao foi utilizado em sinteses posteriores nem nas reaccoes cataliticas. Para obter os monomeros foram ainda utilizadas fosfinas mono ou bidentadas, nomeadamente dppf, DPEPhos, dippf, P(i-Bu)3, P(n-Bu)3, P(CH3)3 ou PhPCl2 que originaram os seguintes complexos neutros ou mono cationicos: [RuCl(dppf)(p-cimeno)]SbF6, [RuI(dppf)(p-cimeno)]SbF6, [RuCl(dppf)(p-cimeno)]BF4, [RuCl(dppf)(p-cimeno)]Cl, [RuCl(P(n-Bu)3)2(p-cimeno)]SbF6, [RuI(P(n-Bu)3)2(p-cimeno)]SbF6, [RuCl(P(i-Bu)3)2(p-cimeno)]SbF6, [RuCl2P(n-Bu)3(p-cimeno)], [RuCl2P(i-Bu)3(p-cimeno)], [RuCl(P(CH3)3)2(p-cymene)]SbF6 e [RuCl2PPh(OCH3)2(p-cymene)]. Entretanto foi ainda sintetizado, por acaso, o dimero [Ru2Cl3(DPEPhos)2(CH3CN)2]SbF6 numa das tentativas de obter o monomero [RuCl(DPEPhos)(p-cymene)]SbF6. Estes compostos foram caracterizados por 1H, 13C e 31P NMR, espectrometria de massa e analise elementar. Entre eles apenas os complexos neutros [RuCl2P(n-Bu)3(p-cimeno)] e [RuCl2P(i-Bu)3(pcimeno)] ja tinham sido referenciados na literatura. As reaccoes aos quais foram submetidos os complexos sintetizados envolvem todas elas, como foi dito, transferencia de hidrogenio. Este tipo de reaccoes envolve normalmente a reducao de cetonas ou iminas e a oxidacao de alcoois ou aminas em que um catalisador transfere hidrogenio entre entre o substrato e o dador ou aceitador de hidrogenio, respectivamente. As reaccoes de transferencia de hidrogenio que aqui foram testadas foram a alquilacao da t-butilamina com alcool feniletilico designada formalmente por “redox neutral alkylation” e a reducao da acetofenona e do benzaldeido aos respectivos alcoois. O potencial catalitico dos complexos sintetizados para com as reaccoes mencionadas foi avaliado maioritariamente por 1H NMR pela percentagem de alcool de partida convertido a produto e num dos casos foi avaliado por cromatografia gasosa pela monitorizacao da concentracao de produto ao longo do tempo. Nomeadamente foi avaliado o potencial catalitico dos dimeros, dos dimeros na presenca de fosfinas e dos monomeros. Na alquilacao da t-butilamina os dimeros por si mesmo revelaram-se inapropriados uma vez que nao foram obtidas conversoes acima de 3%. Ja no caso dos dimeros na presenca de fosfinas os resultados foram significativamente melhores com o par [RuCl2(pcimeno)] 2-DPEPhos a merecer lugar de destaque uma vez que apresentou 96% de alcool de partida convertido a produto com uma proporcao substrato/catalisador de 20. Este resultado foi mesmo o melhor de entre todas as reaccoes de alquilacao levadas a cabo. Relativamente ao uso dos monomeros como pre-catalisadores, o monomero [RuI(dppf)(pcimeno)] SbF6 apresentou o resultado mais promissor com 85% de conversao com uma proporcao substrato/catalisador de 40. Estes resultados tornam-se ainda mais interessantes se levarmos em conta de que estas reaccoes foram levadas a cabo em contacto com a atmosfera, sem desarejamento ou uso de gas inerte durante a reaccao o que nao e a abordagem normalmente encontrada na literatura e que pode ser muito apelativa do ponto de vista industrial. De uma maneira geral as fosfinas bidentadas levaram a resultados promissores tanto quando usadas em combinacao com os dimeros tanto quando foram incorporadas nos respectivos monomeros. O mesmo nao pode ser dito das fosfinas monodentadas. A fosfina P(i-Bu)3 quando na presenca do dimero [RuCl2(p-cimeno)]2 levou a uma conversao de alcool a amina de apenas 28% e quando incorporada no respecivo monomero [RuCl(P(i-Bu)3)2(p-cimeno)]SbF6 nao foi alem dos 9%. Os outros complexos contendo fosfinas monodentadas e que foram testados nesta reaccao de alquilacao, nomeadamente o [RuI(P(n-Bu)3)2(p-cimeno)]SbF6, [RuCl2P(n-Bu)3(p-cimeno)], e o [RuCl(P(CH3)3)2(p-cymene)]SbF6 nao formaram qualquer especia activa cataliticamente uma vez que nao foi detectada a formacao de qualquer amina. Nesta reaccao, para alem da analise do efeito da fosfina, foi analisado o efeito do halogeneto e de uma maneira geral a presenca de iodo em vez de cloro tanto nos dimeros como nos monomeros levou a obtencao de maiores precentagens de produto e/ou reducao na quantidade de alcool por reagir. Foi ainda analisado o efeito do contra-iao, nomeadamente entre os monómeros [RuCl(dppf)(p-cimeno)]SbF6, [RuCl(dppf)(p-cimeno)]BF4 e [RuCl(dppf)(p-cimeno)]Cl e o monomero [RuCl(dppf)(p-cimeno)]Cl parece ser o melhor pre-catalisador apresentando 82% de amina obtida com uma proporcao substrato/catalisador de 20. Os resultados sugerem ainda que os complexos de formula molecular [RuX(LL)(p-cimeno)]+ onde X = halogeneto e LL = ligando bidentado sao os precursores cataliticos nas reaccoes em que sao empregues os dimeros [RuX2(p-cimeno)]2 e fosfinas bidentadas. Uma das reaccoes de alquilacao, como dito anteriormente, foi monitorizada por cromatografia gasosa. Nesta reaccao foi empregue o dimero [RuCl2(p-cimeno)]2 na presença de dppf e a monitorizacao decorreu durante 24h, isto e, o tempo a que todas as alquilações foram submetidas. No entanto esta reaccao apresentou concentracoes de produto/ conversoes muito abaixo das esperadas comparativamente a conversao obtida por 1H NMR para a mesma reaccao. Apesar disso, o padrao de reducao da concentracao de alcool e o padrao de aumento da concentracao de produto ao longo do tempo, corroboram uma das observacoes feitas acerca das conversoes obtidas por 1H NMR, nomeadamente de que durante a reaccao se esta a formar um produto secundario, nomeadamente o ester PhCH2CH2O2CCH2Ph que resulta da reaccao do aldeido formado cataliticamente com o álcool remanescente em solucao que ainda nao reagiu. No entanto, dadas as incoerências encontradas a nivel das concentracoes, da avaria do cromatografo gasoso durante um largo periodo de tempo e de algumas questoes relacionadas com o metodo, a monitorizacao por cromatografia gasosa foi abandonada. Relativamente as reducoes por transferencia de hidrogenio, nomeadamente a reducao da acetofenona e do benzaldeido estas demonstraram padroes de conversao muito semelhantes, nomeadamente os pre-catalisadores que apresentaram percentagens de conversao maiores foram os dimeros sem qualquer adicao de fosfina, ao contrario do que aconteceu nas reaccoes de alquilacao, e a presenca de iodo nos pre-catalisadores nao levou ao aumento, na grande maioria dos casos, da percentagem de produto obtido. No geral, não foram obtidas conversoes acima de 73% o que e um resultado que fica muito aquem dos 100% ja referenciados na literatura para uma larga gama de complexos. Ainda, mais uma vez, as fosfinas monodentadas parecem nao ser apropriadas para serem incorporadas nos pre-catalisadores nas reaccoes de transferencia de hidrogenio uma vez que o monómero [RuI(P(n-Bu)3)2(p-cimeno)]SbF6 nao foi alem dos 3% de acetofenona convertida ao respectivo alcool ou alem dos 12% no caso do benzaldeido. Apesar de tudo, os resultados obtidos permitiram especular um pouco acerca dos mecanismos reaccionais seguidos tendo sido propostos dois mecanismos, um para quando sao empregues apenas os dimeros e outro para quando sao empregues os dimeros na presenca de fosfinas ou empregues os monomeros. Quanto aos resultados obtidos pelo dimero [Ru2Cl3(DPEPhos)2(CH3CN)2]SbF6, este formou especies activas cataliticamente tanto nas alquilacoes como nas reducoes obtendo-se conversoes moderadas em ambos os casos, o que nao deixa de ser um resultado interessante uma vez que, tanto quanto se sabe, ainda nao foi referenciado na literatura o uso de complexos com tres pontes de cloro nas reaccoes em questao.
Scholl, Matthias. "Expanding the Scope of Ruthenium-Based Olefin Metathesis Catalysts". Thesis, 2000. https://thesis.library.caltech.edu/13596/1/scholl-m-2000.pdf.
Texto completo da fonteThe development of well-defined ruthenium alkylidene (PCy₃)₂Cl₂Ru=CHPh brought about a revolution in the area of olefin metathesis. The objective of the work presented here is to expand the scope of ruthenium-based olefin metathesis catalysts such as (PCy₃)₂Cl₂Ru=CHPh through the development of novel synthetic organic methods for ring-closing metathesis as well as through modification of the ligand sphere of the ruthenium complexes.
Chapter 2 describes the application of ruthenium alkylidenes to the catalysis of polycyclization reactions. Several acyclic precursors have been synthesized and reacted with (PCy₃)₂Cl₂Ru=CHPh. These precursors vary in topology and contain acetylenic and/or cycloolefinic metathesis relays. The cyclization reactions proceed in good yields to produce polycyclic polyenes.
Chapter 3 focuses on the synthesis of racemic and enantiopure targets containing the 6,8-dioxabicycIo [3.2.1]octane skeleton using an intramolecular ruthenium-catalyzed ring-closing metathesis reaction as the key step. The natural product frontalin is synthesized in racemic and enantiopure forms and in excellent yields using this methodology.
Chapter 4 outlines the preparation of a novel imidazolylidene-substituted ruthenium-based complex starting from (PCy₃)₂RuCl₂(=CHPh). The N-heterocyclic carbene-substituted olefin metathesis initiator exhibits increased ring-closing metathesis activity at elevated temperature compared to that of the parent complex (PCy₃)₂Cl₂Ru(=CHPh). Di-, tri-, and tetra-substituted cycloolefins are successfully prepared from corresponding diene precursors in moderate to excellent yields.
Chapter 5 describes the preparation of a new family of 1,3-dimesityl-4,5-dihydroimidazol-2-ylidene-substituted ruthenium-based complexes. These air and water tolerant systems exhibit an increased ring-closing metathesis activity at elevated temperature when compared to that of the parent complex (PCy₃)₂Cl₂Ru(=CHPh) as well as to the complexes disclosed previously in Chapter 4. In many instances the activity of these new complexes also rivals or exceeds that of the alkoxy-imido molybdenum-based olefin metathesis catalysts. Applications of chiral N-heterocyclic carbene ruthenium complexes to asymmetric ring-closing metathesis are also briefly discussed.
Finally, the synthesis of the Schiff base-substituted ruthenium carbene complexes on a solid support is described in Chapter 6. The activities of the supported complexes are compared to those of their unsupported counterparts. The newly prepared systems are found to be highly stable to air, moisture, and temperature, and exhibit increased catalytic activity in acidic media.
Savka, Roman. "Synthesis and Application of New Ruthenium-Based Olefin Metathesis Catalysts". Phd thesis, 2014. https://tuprints.ulb.tu-darmstadt.de/3947/1/Savka_PhD%20Thesis.pdf.
Texto completo da fonteLee, Yen-Chun, e 李彥君. "Synthesis and Design of Ruthenium-Based Olefin Metathesis Catalysts Scavenger". Thesis, 2018. http://ndltd.ncl.edu.tw/handle/k7yw5p.
Texto completo da fonte國立中山大學
化學系研究所
106
Grubbs catalyst is one of the most widely used olefin metathesis catalysts. Since ring-opening metathesis(ROM)and ring-closing metathesis(RCM)are the reverse reaction of each other, if the reaction was left for too long, the undesired reverse reaction may occur. In other cases, oligomers may be formed causing the low yield. Metal scavengers can deactivate the catalyst at the right time and can be useful for subsequent purification. In this thesis, silica nanoparticles modified with terminal olefins containing thioether functional groups were investigated as potential scavenger for ruthenium-based metathesis catalysts. We envision that the coordination of the chalcogens and olefins with the ruthenium metal in the catalyst would form a stable cyclic intermediate, which results in the poisoning of the catalyst. The used of modified nanoparticle has the advantages of having larger surface area and ease of separation by centrifugation. The effect of the amount of base and reaction time on particle diameter will be discussed. In addition, the method will be discussed to detectmine the quantity of olefinic functional groups modified on nanoparticles per unit weight. These include the hydroboration with catecholborane, and the indirect analysis of the particles using Ellman''s test. Finally, we will discuss the removal efficiency of the ruthenium metal catalyst.
Rosen, Evelyn Louise. "Novel diaminocarbene ligands and their applications in ruthenium-based metathesis catalysts". Thesis, 2010. http://hdl.handle.net/2152/ETD-UT-2010-08-1562.
Texto completo da fontetext
Morgan, John Philip. "Ruthenium-Based Olefin Metathesis Catalysts Coordinated with NHeterocyclic Carbene Ligands: Synthesis and Applications". Thesis, 2003. https://thesis.library.caltech.edu/4208/1/Thesis.pdf.
Texto completo da fonteThe improved synthesis and olefin metathesis activity of N-heterocyclic carbene (NHC)-coordinated ruthenium alkylidenes of the form (NHC)(L)x(Cl)2Ru=CHR (x = 1 or 2) are reported. In order to circumvent the handling of highly sensitive free carbenes, N-heterocyclic carbene "adducts" were prepared in high yields by the reaction of nucleophilic bases with N,N'-diarylimidazolium salts. Most notably, the addition of trichloromethyl anion to N,N'-dimesityl-4,5-dihydroimidazolium chloride produced an air-, moisture-, and temperature-stable crystalline adduct, 2-trichloromethyl-4,5-dihydro-imidazolidine. When this species is heated above the critical temperature of 55 degrees C in the presence of (PCy3)2(Cl)2Ru=CHPh, a single, clean phosphine substitution reaction occurs to form the NHC-coordinated benzylidene (NHC)(PCy)3(Cl)2Ru=CHPh in 84% isolated yield. This procedure has been successfully scaled up to industrial production and remains the most effective catalyst synthesis to date.
The NHC-coordinated catalysts show dramatically expanded activity relative to their bis-phosphine counterparts. The high yielding, trans-stereoselective cross metathesis of various acroyl substrates is the first example of the ruthenium-catalyzed metathesis of olefins directly substituted with electron-withdrawing functionality. Ring-opening cross metathesis of acroyl species with relatively high ring strain cyclooctadiene and norbornene monomers has also been achieved in good yields and perfect regioselectivity when the norbornene is asymmetrically substituted with a bridgehead methyl group.
Further expansion of the substrate scope was achieved when the catalyst's phosphine ligand was replaced with more weakly bound 3-bromopyridine (3-Br-pyr) ligands. The resulting catalyst (NHC)(3-Br-pyr)2(Cl)2Ru=CHPh produced synthetically useful yields (>= 67%) in the cross metathesis of acrylonitrile and terminal olefins (as opposed to less than 30% yield with the phosphine-coordinated catalyst). NHC-coordinated catalysts therefore allow both electron-rich and electron-poor olefins to undergo metathesis in the same pot, potentially leading to synthetically valuable products containing electronically differentiated olefins.
The lower activity of phosphine-coordinated catalysts relative to those coordinated with 3-bromopyridine can be addressed by the addition of "phosphine scavengers" to the former. Higher pKa carboxylic acids (such as acetic and benzoic acids) are capable of accelerating catalysis as effectively as the much stronger hydrochloric acid, without concomitant catalyst decomposition. These properties make carboxylic acids the optimal choice for use with sensitive organic substrates.
Oswin, Chris. "HOMOGENEOUS TRIDENTATE RUTHENIUM BASED HYDROGENATION CATALYSTS FOR THE DEOXYGENATION OF BIOMASS DERIVED SUBSTRATES IN AQUEOUS ACIDIC MEDIA". Thesis, 2013. http://hdl.handle.net/10214/7438.
Texto completo da fonteNSERC
Lin, Jui-Nien, e 林芮年. "Photocatalytic Hydrogen Generation from Alcohols by Ruthenium-Based Biomimetic H-Cluster Catalyst". Thesis, 2017. http://ndltd.ncl.edu.tw/handle/ew93zc.
Texto completo da fonteLien, Wan-HSiang, e 連萬翔. "The Study of a Ruthenium-Based Biomimetic H-Cluster Catalyst for Formic Acid Dehydrogenation and Carbon Dioxide Hydrogenation". Thesis, 2018. http://ndltd.ncl.edu.tw/handle/vv4658.
Texto completo da fonte國立交通大學
生物科技學系
107
The non-renewable energy, which is a limited natural energy that comes from the oil, coal, and natural gas, is not likely to continue into the future. A renewable resource such as hydrogen is the fuel of the future, as it has the highest heat energy of combustion compared to the other organic sources and it is eco-friendly. In nature, hydrogen can be generated by the hydrogenase. In recent years, studies on the hydrogenase have been published, and the investigated hydrogen production systems have been applied. In this study, we successfully synthesized an artificial bionic iron-iron [Fe-Fe] hydrogenase's active site and replace the center metal atom iron with ruthenium, Ru2S2(tosyl-adt2-), and characterized the system using UV-visible spectroscopy, Fourier transform infrared spectroscopy, cyclic voltammetry, nuclear magnetic resonance spectroscopy, and X-ray diffraction. In the experiments, the Ru2S2(tosyl-adt2-) activities were obtained, and aqueous/alcohol/formic acid dehydrogenation under a 500 W Xe lamp was optimized. The effects of temperature, concentration, base, p-ligand, and photosensitizers were studied. Lastly, the lamp source irradiation was replaced by solar irradiation in the best condition. Hydrogen as the fuel of the future requires both safe and stable for storage and transportation. Formic acid is produced by the hydrogenation of CO2, and it is an intermediate H2 and CO2 carrier. Furthermore, we also report the development and optimization of an active system of the reversible hydrogenation of CO2 with the Ru2S2(tosyl-adt2-) catalyst.
Madureira, Joana. "Batch sodium-borohydride hydrolysis in the presence of nickel-ruthenium based catalyst: Addition on biopolymers to improve hydrogen storage in the liquid phase by solubility effects". Dissertação, 2013. http://hdl.handle.net/10216/75055.
Texto completo da fonteMadureira, Joana Sofia Oliveira. "Batch sodium-borohydride hydrolysis in the presence of nickel-ruthenium based catalyst: Addition on biopolymers to improve hydrogen storage in the liquid phase by solubility effects". Master's thesis, 2013. https://repositorio-aberto.up.pt/handle/10216/68536.
Texto completo da fonteMadureira, Joana Sofia Oliveira. "Batch sodium-borohydride hydrolysis in the presence of nickel-ruthenium based catalyst: Addition on biopolymers to improve hydrogen storage in the liquid phase by solubility effects". Dissertação, 2013. https://repositorio-aberto.up.pt/handle/10216/68536.
Texto completo da fonteWang, Ying-Lien, e 王櫻璉. "(I) The Design and Synthesis of Benzimidazole and Dihydroquinazolines Derivatives Based on Lead Compound (II) Ruthenium-Catalysed C-H activation to the Synthesis of [4,5]imidazo[2,1-a]isoindole Derivatives". Thesis, 2016. http://ndltd.ncl.edu.tw/handle/71056344608467361199.
Texto completo da fonte