Дисертації з теми "Phosphine Complex"
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Larkin, Scott A. "Synthesis and Supermolecular Chemistry of Biphenylthioatogold(I)Phosphine Complexes." Fogler Library, University of Maine, 2007. http://www.library.umaine.edu/theses/pdf/LarkinSA2007.pdf.
Повний текст джерелаLugan, Noël. "Clusters du ruthenium a ligands assembleurs : stabilite, reactivite." Toulouse 3, 1987. http://www.theses.fr/1987TOU30156.
Повний текст джерелаSinha, Pankaj. "Phosphorescent Emissions of Coinage Metal-Phosphine Complexes: Theory and Photophysics." Thesis, University of North Texas, 2009. https://digital.library.unt.edu/ark:/67531/metadc12200/.
Повний текст джерелаSinha, Pankaj Omary Mohammad A. "Phosphorescent emissions of coinage metal-phosphine complexes theory and photophysics /." [Denton, Tex.] : University of North Texas, 2009. http://digital.library.unt.edu/ark:/67531/metadc12200.
Повний текст джерелаRies, Michel. "Synthese et reactivite de clusters heterometalliques contenant le ligand assembleur ph : :(2)pch::(2)pph::(2)." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13208.
Повний текст джерелаBLUM, THIERRY. "Synthese et reactivite de complexes heterometalliques a ligand (s) phosphure (s)." Université Louis Pasteur (Strasbourg) (1971-2008), 1989. http://www.theses.fr/1989STR13078.
Повний текст джерелаDelavaux, Béatrice. "Complexes heterobimetalliques hydrures (ru-m) (m=rh,ir,cu) a ligands bisdiphenylphosphinomethane : synthese et reactivite." Toulouse 3, 1986. http://www.theses.fr/1986TOU30078.
Повний текст джерелаGomes, de Lima Bernardes Miriam. "Réactivité de complexes organométalliques mono- et dinucléaires : synthèse de thiolato-composés du molybdène, du tungstène et du cobalt : étude de la formation de liaisons c-c dans la sphère de coordination du métal." Brest, 1986. http://www.theses.fr/1986BRES2008.
Повний текст джерелаRatcliffe, Shane. "Cocrystals of urea, complex chemistry of thioureas with group 15 halides and halogen adducts of tertiary phosphine selenides." Thesis, University of Manchester, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.706079.
Повний текст джерелаAmawi, Rema Mouawya Klausmeyer Kevin Kenneth. "Synthesis and characterization of silver(I) salts with amino methyl pyridines containing phosphines novel complex formation upon ratio, anion, or ligand changes /." Waco, Tex. : Baylor University, 2008. http://hdl.handle.net/2104/5180.
Повний текст джерелаGOMES, DE LIMA LUIS CARLOS. "Reactions d'alcynes cyanes (monocyanoacethylene et dicyanoacethylene), vis-a-vis de complexes organometalliques du fer, du cobalt, du molybdene et du tungstene." Brest, 1986. http://www.theses.fr/1986BRES2009.
Повний текст джерелаAlnagi, Omar. "Reaction de la trimethylphosphine sur les sels de cobalt (ii) : synthese des complexes pentacoordonnes cox::(2)(pme::(3))::(3) (x=c1**(-), br**(-), i**(-), ncs**(-), no::(2)**(-)), reactivite vis-a-vis de petites molecules co, no et o::(2)." Toulouse 3, 1987. http://www.theses.fr/1987TOU30048.
Повний текст джерелаRimmelin, Jean. "Etude des relations structure-reactivite electrochimique dans quelques clusters du cobalt et du rhodium." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13176.
Повний текст джерелаFeng, Liwen. "Chemical tools for antimalarial drug development : synthesis of plasmodione analogues and 13C-enriched plasmodione for drug metabolomics investigations." Thesis, Strasbourg, 2017. http://www.theses.fr/2017STRAF038.
Повний текст джерелаMalaria is a tropical parasitic disease threatening populations in tropical and sub-tropical areas, especially young children in Africa. Due to the drug resistance spread all over the world in the past 50 years, new drugs are urgently needed. Plasmodione (benzylmenadione series) had been identified as a potent anti-malarial early lead drug, acting through a redox bioactivation on asexual and young sexual blood stages, but its drug metabolism is unknown. Therefore, in order to identify the structures of the active drug metabolites generated from the antimalarial plasmodione, fully 13C18-enriched-plasmodione synthesis was designed and performed in 10 steps. Furthermore, the extraction method for the drug metabolism study was established from 13C18-enriched plasmodione-treated parasitized red blood cells. On the other hand, the preparation of oxetane and N-alkylaryl derivatives of plasmodione with potential improved solubility was also investigated through aromatic nucleophilic substitution (SNAr) and palladium-catalyzed Buchwald-Hartwig coupling reaction, respectively. Finally, a gold(I) phosphole complex, known as an irreversible and potent inhibitor of the human seleno-dependent thioredoxin reductase, was synthetized and its antiparasitic profile investigated against a panel of parasites, protozoans and helminthes in cultures
Theulier, Cyril Alexis. "Ligands ambiphiles et coopérativité métal - acide de Lewis." Thesis, Toulouse 3, 2021. http://www.theses.fr/2021TOU30013.
Повний текст джерелаThe present work is dedicated to the study of metal/Lewis cooperativity. Over years gold has proven its reluctance to undergo elementary steps classicaly disclosed in the coordination chemistry of transition metals. The initial concept behind this research project consist in the installation of a Lewis acid in the first coordination sphere through the coordination of ambiphilic ligands. The ultimate objective is to take full advantage of the assistance provided by the acceptor to extol the reactivity at gold and achieve challenging transformations. The introductive chapter delivers a bibliographic overview of the organometallic chemistry encountered with gold. A peculiar interest is paid to the limitations araising from an intrinsic difficulty to access high oxidation state. The coordination chemistry of ambiphilic ligands is subsequently introduced. The relation between the coordination mode of the ligand and the reactivity of the ensuing complexe is highlighted. To support this research a new mono-ortho-phenylene-phosphinoborane bearing an extremely Lewis acidic boron has been developed. The second chapter brings forward the synthesis of neutral species by coordination of the ambiphilic ligand on gold(I) aryl, methyl and trifluoromethyl complexes. The presence in those species of a gold to boron dative interaction (Z interaction) allowed to assess and discuss the sigma-acceptor ability of the new ligand. Then their reactivity towards oxidative addition has been studied. The third chapter results from a serendipitous discovery made over attemts to generalize the former reactivity. The phosphine borane was found to react with gold(I) alkynyl and alkenyl complexes. via a stereo and regioselective 1,1-phosphaboration process. Zwitterionic complexes stemming from a migration of the organic fragment from the gold to the boron have been authenticated as key intermédiates. Kinetic and DFT investigations suggest a stepwise pathway including the decoordination of the phosphine followed by the anti nucleophilic attack to the unsaturated bond henceforth activated by gold. The boron center acts as a relay and tether for the organic moiety. The last chapter is devoted to the Au(III)/Au(I) reductive elimination. The complexation of a mono-ortho-phenylene-phosphinoborane has shown to foster the challenging C(sp3)-C(sp3) reductive coupling. Kinetic studies emphasised a strong impact of the ligand's Lewis acidity supporting the participation of the acceptor in the mechanism. DFT calculations were performed to elucidate the mechanism and shed light onto a gold/Lewis acid cooperativity
Rahmouni, Noureddine. "Synthese et reactivite de complexes dinucleaires des metaux de transition." Université Louis Pasteur (Strasbourg) (1971-2008), 1986. http://www.theses.fr/1986STR13080.
Повний текст джерелаJund, Rodolphe. "Electrochimie de clusters mixtes tetrametalliques." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13175.
Повний текст джерелаNemra, Ghinwa. "Comportement electrochimique de nouveaux complexes a liaison pd-pd et pt-pd stabilises par des ligands bidentates ph : :(2)pch::(2)pph::(2)." Strasbourg 1, 1986. http://www.theses.fr/1986STR13055.
Повний текст джерелаChan, Wing-han, and 陳詠嫻. "Coordination chemistry of the pyridyl, naphthyridyl and [alpha], [omega]-polyether phosphine ligands and x-ray crystal structures andspectroscopic properties of the metal complex derivatives." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1998. http://hub.hku.hk/bib/B31236595.
Повний текст джерелаArliguie, Thérèse. "Complexes du ruthenium hydrures et derives de l'hydrogene moleculaire : reactions de deshydrogenation inter et intramoleculaires." Toulouse 3, 1988. http://www.theses.fr/1988TOU30111.
Повний текст джерелаGourdon, André. "Synthèse et étude structurale de clusters de fer contenant un hétéroatome du type carbure, nitrure, phosphure." Paris 6, 1986. http://www.theses.fr/1986PA066404.
Повний текст джерелаChan, Wing-han. "Coordination chemistry of the pyridyl, naphthyridyl and [alpha], [omega]-polyether phosphine ligands and x-ray crystal structures and spectroscopic properties of the metal complex derivatives /." Hong Kong : University of Hong Kong, 1998. http://sunzi.lib.hku.hk/hkuto/record.jsp?B19481640.
Повний текст джерелаRouida, Bouchaïb. "Syntheses diastereoselectivites de complexes chiraux du molybdene et du fer carbonyle par action de derives asymetriques du phosphore." Paris 6, 1988. http://www.theses.fr/1988PA066515.
Повний текст джерелаTouma, Marwan. "Nouvelles reactions d'oligomerisation et de telomerisation selectives catalysees par des complexes cationiques du palladium." Toulouse 3, 1986. http://www.theses.fr/1986TOU30139.
Повний текст джерела李慧敏 and Huai-min Li. "Photochemical studies of binuclear platinum and rhodium complexes withbridging isocyanide, phosphite and phosphine ligands." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1989. http://hub.hku.hk/bib/B31231603.
Повний текст джерелаSwor, Charles D. (Charles David) 1982. "Synthesis, coordination chemistry, and reactivity of functionalized phosphines: Toward water-soluble macrocyclic phosphine complexes." Thesis, University of Oregon, 2011. http://hdl.handle.net/1794/11264.
Повний текст джерелаMacrocyclic phosphine compounds have long been sought as ligands for transition metal complexes because of their strong binding properties. Despite considerable effort in this field, no general methods for synthesizing phosphine macrocycles or their complexes have been developed. This dissertation describes attempts to synthesize an iron complex with a water-soluble macrocyclic tetraphosphine ligand for use in separating nitrogen from natural gas. Chapter I reviews previous syntheses of macrocyclic phosphine ligands and their complexes, focusing on ligand synthesis, coordination chemistry, and demetallation of the complexes. Chapter II reports on the synthesis of water-soluble secondary bidentate phosphine ligands, their coordination chemistry with iron(II), and attempts to use these complexes as templates for forming a macrocyclic iron-phosphine complex by reactions with carbon electrophiles. Over the course of treating these iron complexes with various carbon electrophiles, an interesting reaction between bromomaleic anhydride and proton sponge was discovered. Chapter III explores the product, 4-maleicanhydrido-1,8-bis-(dimethylamino)naphthalene (MAPS). Due to its conjugated donor-acceptor network, which is disrupted upon protonation, MAPS acts as a colorimetric version of a proton sponge. The attachment of MAPS to amine-functionalized solid supports, forming solid-supported proton sponge reagents, is also described. Chapter IV discusses the synthesis of an iron(II) complex of the water-soluble phosphine 1,2-bis(di(hydroxymethyl)phosphino)ethane (DHMPE). Although unbound hydroxymethylphosphines commonly react with NH-functional amines via the phosphorus Mannich reaction, this and other complexes of DHMPE do not undergo this reaction. Further investigation with hydroxymethylphosphine-boranes suggests that the currently-accepted mechanism of the phosphorus Mannich reaction is incorrect, and an alternate mechanism is proposed. Chapter V discusses the synthesis and functionalization of copper(I) complexes of water-soluble phosphines. Unlike the complexes described in Chapter I, these complexes readily react with α,ω-dihalides or di(acyl chloride)s, forming complexes whose mass spectra correspond to those with macrocyclic phosphine ligands. Unlike most macrocyclic tetraphosphine complexes, these complexes can be demetallated by treatment with sulfide. Finally, a new synthesis of water-soluble macrocycles, based on lessons learned during the course of these investigations, is proposed. This dissertation includes previously published and unpublished co-authored material.
Committee in charge: Dr. Michael M. Haley, Chairperson; Dr. David R. Tyler, Advisor; Dr. Darren W. Johnson, Member; Dr. Shih-Yuan Liu, Member; Dr. Mark H. Reed, Outside Member
Sivade, Alain. "EVALUATION DE PHOSPHINO-TRIS(m-METAPHENYLSULFONATES) EN CATALYSE D'OLIGOMERISATION ET DE TELOMERISATION AU CONTACT DE COMPLEXES DU NICKEL OU DU PALLADIUM." Toulouse 3, 1987. http://www.theses.fr/1987TOU30221.
Повний текст джерелаHoriuti, Toshihide. "Studies on Enantioselective Addition to C=C Bonds Catalyzed by Transition Metal-Phosphine-Phosphite Complexes." Kyoto University, 1997. http://hdl.handle.net/2433/202317.
Повний текст джерелаLi, Huai-min. "Photochemical studies of binuclear platinum and rhodium complexes with bridging isocyanide, phosphite and phosphine ligands /." [Hong Kong] : University of Hong Kong, 1989. http://sunzi.lib.hku.hk/hkuto/record.jsp?B12428541.
Повний текст джерелаCai, Feng Xian. "Influence du coordinat triéthylphosphine sur la réactivité des ions Ni+ supportés dans la réactivité d'oligomérisation de l'éthylène." Paris 6, 1986. http://www.theses.fr/1986PA066077.
Повний текст джерелаDunn, P. "Synthesis and reactivity of phosphido and phosphidine bridged heteronuclear alkylidyne cluster compounds." Thesis, University of Bristol, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.233578.
Повний текст джерелаPope, Simon Johnathan Albert. "Syntheses and studies on transition metal complexes involving phosphine ligands towards the syntheses of macrocyclic phosphines." Thesis, University of Southampton, 1999. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.302349.
Повний текст джерелаPike, Sebastian David. "Investigating the chemistry of cationic rhodium bisphosphine complexes : comparing reactivity in the solid state with solution." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:413c8a57-0a5e-4e51-8874-e48db8079675.
Повний текст джерелаDjiele, Ngameni Patrice. "Phosphane and Phosphite Silver(I) Complexes: Synthesis, Reaction Chemistry and their Use as CVD Precursors." Doctoral thesis, [S.l. : s.n.], 2005. http://archiv.tu-chemnitz.de/pub/2005/0008.
Повний текст джерелаPlancq, Sabine. "Heteronuclear carbonyl phosphine complexes." Thesis, Heriot-Watt University, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.335276.
Повний текст джерелаChavagnan, Thierry. "Resorcinarenic phosphines and iminophosphoranes for catalysis : formation of capsular complexes." Thesis, Strasbourg, 2016. http://www.theses.fr/2016STRAF023/document.
Повний текст джерелаThis thesis describes the synthesis of three types of phosphorus-containing resorcinarene cavitand: a) compounds with diphenylphosphino groups grafted to the wider rim of a generic cavity. These phosphines undergo facile, directed C–O bond breaking upon reaction with transition metal ions in the presence of exogenous or endogenous nucleophiles. A nickel complex of this type was shown suitable for the low pressure production of short α-olefins starting from ethylene; b) cavitands distally-substituted by two iminophosphoranyl groups (–Ph2P=NAr). One of them (Ar = p-anisyl), when combined with Rh(I), resulted in a shape-selective olefin hydrogenation catalyst; 3) double phosphino-cavitands, which upon chelation gave metallo-capsular complexes in which the metal centre is either fully or partially embedded in the resulting cavity. A platinum complex of this type resulted in the selective hydroformylation of styrene into the expected branched aldehyde
Regragui, Rachid. "Synthèse de complexes mixtes ruthénium-cobalt à pont phosphido : réactions sélectives de phosphines et d'alcynes." Rennes 1, 1986. http://www.theses.fr/1986REN10038.
Повний текст джерелаLavender, Mark Harley. "Phosphine stabilised di-iron complexes." Thesis, University College London (University of London), 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.283749.
Повний текст джерелаWells, F. J. "Tertiary phosphine complexes of vanadium." Thesis, Imperial College London, 1987. http://hdl.handle.net/10044/1/46906.
Повний текст джерелаEl, Harouch Yamna. "Applications des complexes zirconocènes et des hétéroéléments en synthèse organique et organométallique." Toulouse 3, 2004. http://www.theses.fr/2004TOU30216.
Повний текст джерелаThe first chapter is the development object bibliographical of the various aspects of the synthesis, structure and reactivity of amidins. The second chapter describes the réductif coupling of acetylenic Ph2P-Co̱C-SiMe3 and Me2N-Co̱C-Ph with the benzyne zirconocene and/or the complex irconacyclopropane. The structure of the complexes zirconocenes obtained in the various reactions of coupling highlight the major role of the steric and electronic properties of the groupings silyle, phosphino, and amino. The third chapter relates to the synthesis of the zirconiés a-diazoi͏̈ques complexes with reaction of azazirconaindenes with the compounds of the type HC(N2)R. The study of the reactivity of these complexes with respect to various reagents was approached. The final chapter is devoted to the synthesis and the study of the reactivity of N-phosphinoformamidines R2N-CH=N-PR'2. The nature of the products which result from the addition of different electrophiles on R2N-CH=N-PR'2 depends largely on the R' groupings. According to the temperature and polarity of the reactional medium, we observed a process "isomerism of enchaînement", after addition of R2PCl on the formamidines
Cuevas-Chávez, Cynthia. "Synthèse, structure et réactivité de complexes de platine et d'iridium à ligands phosphinodi(benzylsilanes)." Thesis, Toulouse 3, 2019. http://www.theses.fr/2019TOU30196.
Повний текст джерелаThe rich chemistry and applicability in such a wide range of fields (e.g. small molecule activation, selective transformations including catalytic developments, etc.) of silicon based pincer-like compounds with transition metals has been witnessed by the remarkable advances in coordination chemistry as well as in organometallics. This is due to the outstanding properties of Si atoms which generate electron rich metal centres concomitantly labilizing trans substituents. However, despite all the plethora of arrangements of such species throughout the literature (e.g. framework, number and nature of anchoring points), metal derivatives with polydentate ligands incorporating two silicon atoms are limited as is the study of their reactivity. Therefore, this thesis presents the synthesis, structure and reactivity of novel Platinum and Iridium complexes supported by the "SiPSi" pincer-type ligand. Interestingly, the square-planar PtII complex of formula trans-[(SiPSi)Pt(PPh3)] (SiPSi = P(o-C6H4CH2SiMe2)2Ph) reversibly reacts with small molecules, H2 and CO, forming the corresponding dihydride and dicarbonyl 18-electron species, respectively. On the other hand, the dimeric complex [Ir(SiPSi)(µ-Cl)]2 dissociates in benzene solution to yield the 14-electron monomeric species [Ir(SiPSi)Cl] which readily reacts with two electron donors. 16- and 18-electron configurations are obtained depending mainly on sterics in the case of P-derivatives. Different dispositions of L ligands on 18-electron species (L = CNCD3, CO) and isomerisation processes were also evidenced. Moreover, even if iridium is prone to perform oxidative additions, we also showed that Si-H agostic bonding can favour C-H activation of an adjacent acidic methylene group leading to a tetradentate ligation
Cartwright, Jonathan. "Organometallic chemistry of ruthenium phosphine complexes." Thesis, University of Warwick, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.307976.
Повний текст джерелаNorman, Timothy. "Imido and phosphine bridged organometallic complexes." Thesis, University College London (University of London), 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.243522.
Повний текст джерелаMorton, David Alexander Vodden. "Structural studies of metal phosphine complexes." Thesis, University of Bristol, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.303770.
Повний текст джерелаMalbosc, François. "Étude, dans divers complexes du rhodium (I), du mode de coordination des ligands tris(pyrazolyl)borate substitués : réactivité vis à vis des liaisons NH et CCL du complexe [TpMe²,⁴CLRh(CO)₂]." Toulouse, INPT, 1999. http://www.theses.fr/1999INPT003C.
Повний текст джерелаCieślikiewicz-Bouet, Monika. "Synthesis, structural investigations and evaluation of pyrazine sensitizers for lanthanides emitting in near-infrared and novel phosphine derivatives." Thesis, Orléans, 2012. http://www.theses.fr/2012ORLE2088.
Повний текст джерелаOn account of the ubiquity of nitrogen heterocycles and their biological properties, the great attention is paid to developing methodologies of their synthesis and functionalization. For this purpose, the study of functionalization of enamides constitutes an important topic due to the utility of these motifs in the construction of complex heterocyclic derivatives. Palladium-catalyzed reactions of cross- coupling are rapid and efficient methods of choice for synthesis of enamides particularly starting from enol phosphates derived from lactams, imides or amides. The first chapter of the thesis evokes the original C-P coupling reaction of chiral and achiral secondary phosphine boranes with different enol phosphates in mild reaction conditions, leading to corresponding enamido-phosphine boranes. This methodology permits the construction of libraries of novels phosphines. Also, the reaction of nucleophilic addition of phosphide anions onto various enecarbamates acyclic was elaborated, giving an access to original beta-phosphino alpha-amino acids, bearing the quaternary carbon on alpha position to nitrogen. The second chapter is devoted to the preparation and characterization of organic chromophores based on the pyrazinic core, which are likely to exhibit the fluorescence properties. These compounds were designed to form new sensitizing systems for lanthanide cations and could be used as organic sensitizers for molecular imaging in near infrared
Francisco, Thiago dos Santos. "Complexos fosfínicos de rutênio com ligantes o-fenilênicos: síntese, caracterização e aplicação como catalisadores em reação de hidrogenação." reponame:Repositório Institucional da UFC, 2010. http://www.repositorio.ufc.br/handle/riufc/20122.
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The dependence on the experimental conditions of the production of phosphine ruthenium complexes containing o-phenylene ligands was analyzed in this work. The reaction between mer-[RuIIICl3(dppb)(H2O)] and [RuIICl2(dppb)(PPh3)] starting complexes, where dppb = 1,4-bis(diphenylphosphine)butane and PPh3 = triphenilphosphine, and 4-cloro-1,2-phenylenediamine (opda-Clcat), 3,3’,4,4’-tetraaminebiphenyl (tabcat,cat), benzenedithiol (bzditiolcat), and 9,10-phenantrequinone (fenantq) species resulted in the production of trans-[RuIICl2(dppb)(opda-Clcat)], cis-[RuIICl2(dppb)(opda-Clq)], trans-[RuIICl2(dppb)(tabq,cat)], cis-[RuIICl2(dppb)(tabq,cat)], trans-[RuIICl2(dppb)(Bzditiolcat)], and trans-[RuIICl2(dppb)(fenantq)] complexes. These compounds were characterized by means of electrochemical techniques, electronic and vibrational spectroscopies, and 31P{1H} nuclear magnetic resonance. The 31P{1H} NMR technique allowed the determination of the cis and trans isomers based on correlation with previously reported data and with the isolated compounds from the syntheses made from the [RuIICl2(dppb)(PPh3)] reduced starting complex. The mechanistic scheme for the reaction between the mer-[RuIIICl3(dppb)(H2O)] complex and the opda-Clcat ligand was proposed based on kinetics experiments acquired by using stopped-flow technique. In accordance with the kinetic results, there is the suggestion of the formation of a binuclear intermediate whose metal centers are reduced through an intra-molecular electron transfer process where the ligand is oxidized. This conclusion reinforces the results reported in the literature for the opda ligand. All the synthesized complexes presented catalytic activity toward the hydrogenation reaction of acetophenone molecule. Among these, based on preliminary results, the cis-[RuIICl2(dppb)(opda-Clq)], trans-[RuIICl2(dppb)(tabq,cat)], and cis-[RuIICl2(dppb)(tabq,cat)] complexes presented a conversion of 100%. Although a more careful study should be done, this result suggests that these compounds are able to act as catalysts in reduction reaction of polar double bonding.
A influência das condições reacionais na formação de complexos fosfínicos de rutênio com ligantes o-fenilênicos foram estudadas neste trabalho. A reação dos complexos mer-[RuIIICl3(dppb)(H2O)] e [RuIICl2(dppb)(PPh3)], onde dppb = 1,4-bis(difenilfosfina)butano e PPh3 = trifenilfosfina, e os ligantes o-fenilênicos 4-cloro-1,2-fenilenodiamina (opda-Clcat), 3,3’,4,4’-tetraaminobifenil (tabcat,cat), benzenoditiol (bzditiolcat) e 9,10-fenantrequinona (fenantq) resultaram na formação dos complexos trans-[RuIICl2(dppb)(opda-Clcat)], cis-[RuIICl2(dppb)(opda-Clq)], trans-[RuIICl2(dppb)(tabq,cat)], cis-[RuIICl2(dppb)(tabq,cat)], trans-[RuIICl2(dppb)(Bzditiolcat)] e trans-[RuIICl2(dppb)(fenantq)]. A caracterização destas espécies foi realizada por técnicas eletroquímicas, espectroscopias eletrônica e vibracional e ressonância magnética nuclear de 31P{1H}. A técnica de RMN 31P{1H} permitiu a identificação dos isômeros cis e trans dos complexos sintetizados através de comparação com dados da literatura e com espectros obtidos para os produtos isolados a partir do complexo reduzido, [RuIICl2(dppb)(PPh3)]. A proposta mecanística para a reação entre o complexo mer-[RuIIICl3(dppb)(H2O)] e o ligante opda-Clcat foi baseada em experimentos cinéticos obtidos através da técnica de stopped-flow. De acordo com os resultados cinéticos, há a sugestão de formação de um intermediário binuclear cujos centros metálicos são reduzidos através de um processo de transferência de elétrons intramolecular onde o ligante sofre oxidação. Esta conclusão reforça os resultados reportados na literatura para o ligante opda. Todos os complexos sintetizados apresentaram atividade catalítica em relação à reação de hidrogenação da molécula de acetofenona sendo que, de acordo com os ensaios realizados, os complexos cis-[RuIICl2(dppb)(opda-Clq)], trans-[RuIICl2(dppb)(tabq,cat)] e cis-[RuIICl2(dppb)(tabq,cat)] apresentaram uma conversão de 100%. Embora seja necessário um estudo mais criterioso, este resultado sugere que estes compostos podem atuar como catalisadores de reação de redução de duplas ligações polares.
Henderson, Steven G. D. "Spectroscopic studies of platinum halo-phosphine complexes." Thesis, University of Edinburgh, 1986. http://hdl.handle.net/1842/28226.
Повний текст джерелаDouglas, Thomas Mark. "Chemistry of cationic rhodium alkyl phosphine complexes." Thesis, University of Oxford, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.504386.
Повний текст джерелаMerle, Nicolas. "Transition metal complexes of chelating phosphine boranes." Thesis, University of Bath, 2006. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.426296.
Повний текст джерела