Dissertations / Theses on the topic 'P-N ligands'
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1
Pop, Lucian-Cristian. "Pnictogénium cations (P, As, Sb) et germylènes à ligands N,N’ et N,O-chélatants : synthèse, étude structurale et réactivité." Toulouse 3, 2010. http://thesesups.ups-tlse.fr/1517/.
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Ce travail concerne la stabilisation d'espèces à basse coordinence du groupe 15 (P, As et Sb) et du germanium par des substituents N,N' et N,O chélatants comportant un système pi-conjugué comme les aminotroponiminate et aminotroponate. Le premier chapitre porte sur la mise au point des voies de synthèse de composés dichlorés ou de chloropnictogénium cations. L'étude par RMN multinoyaux (1H, 13C et 31P) des pnictogénium cations a montré une bonne délocalisation de la charge positive sur le cycle insaturé à 7 chaînons ce qui a été confirmé par l'étude de leur structure par diffraction des rayons X et des calculs DFT. Dans le deuxième chapitre, nous avons réalisé des réactions caractéristiques comme des réactions d'oxydation. Les phosphénium cations conduisent très facilement aux composés hydroxylés correspondants. Une réaction inattendue d'élimination de HCl a conduit à des dioxo- et thiooxo-phosphoranes qui constituent les premiers exemples d'aminométa phosphonate (et de son équivalent soufré) stabilisés par complexation intramoléculaire. Les réactions de cycloaddition avec une o-quinone ont également permis d'accéder à de nouveaux cycloadduits. La dernière partie de ce chapitre porte sur l'aptitude de ces phosphéniums cations à former des complexes avec les métaux de transition. Nous avons pu ainsi isoler le premier hydroxyphosphénium stabilisé par complexation avec le tungstène. Dans le troisième chapitre, nous avons développé l'étude de nouveaux systèmes chélatants: les di-amonitroponimines et di-aminotropones pontées. Nous avons ensuite réalisée une extension de ces réactions au germanium et pu ainsi accéder à de nouveaux bis-germylènes. Ces espèces bien que tri-coordinnées conservent leur caractère divalent comme le montrent leurs réactions de cycloaddition avec une o-quinone. Enfin, un bis-germylène complexé par le tungstène a pu être isolé et sa structure déterminée par diffraction des rayons XThis thesis entitled "N,N'- and N,O-chelated pnictogenium cations (P, As, Sb) and germylenes: syntheses, structural studies and reactivity" is structured in three chapters. In the first chapter an easy and direct route to the first phosphenium and arsenium cations supported by N,N' or N,O-chelation derived from a tropolone scaffold was presented. These new compounds were fully characterized by various spectroscopic methods, X-ray analyses and DFT calculations. The expected Lewis amphoterism which is illustrated on the one hand, by the high-lying phosphorus lone-pair orbital (HOMO-1), and on the other hand, by the delocalized positive charge opens up new perspectives for the involvement of these ambiphilic species as valuable ligands for new catalysts. The second chapter concerns the reactivity of these new pnictogenium cations. A variety of reactions including oxidation (with dimethylsulfoxide, sulfur or selenium), cycloaddition and halide ion extraction were studied. The first example of an aminometaphosphonate (and its sulfur equivalent) stabilized by intramolecular complexation was reported. For the first time, a hydroxyphosphenium cation stabilized by complexation with pentacarbonyltungsten was prepared and its structure elucidated by X-ray single-crystal diffraction study. The last chapter refers to the synthesis and characterization of bridged bis(pnictogenium) cations with an extension to divalent germanium compounds. Among the most noteworthy result is the stable bis-germylene pentacarbonyl tungsten complex
2
Irele, Patricia Taiwo. "Some chemistry of triosmium clusters with P- and N- ligands." Thesis, University of Cambridge, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.254120.
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Sauthier, Mathieu. "1,2-diiminophosphoranes et 2-'2-pyridyl)phospholes : : nouveaux ligands N,N et P,N pour la catalyse homogène." Rennes 1, 2001. http://www.theses.fr/2001REN10040.
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Nous décrivons la synthèse de nouveaux ligands N,N chiraux : les 1,2-diiminophosphoranes. La chimie de coordination de ces ligands dépend de la nature du squelette carboné. Leur utilisation pour la réaction de substitution allylique catalysée par le palladium a permis d'obtenir de bons excès énantiomériques. Ils ont été utilisés pour la préparation de complexes de nickel qui s'avèrent être des catalyseurs très actifs pour la réaction d'oligomérisation de l'éthylène. Nous avons également préparé de nouveaux ligands mixte P,N : les 2-(2-pyridyl)phospholes. Ces composés se comportent comme des chélates vis à vis du palladium et du ruthénium. Les complexes cationiques du palladium sont actifs pour la copolymérisation éthylène-monoxyde de carbone. Les 2,5-di(2-pyridyl)phospholes possèdent une chimie de coordination très originale et conduisent à la formation de systèmes bimétalliques possédant une phosphine pontante symétrique.
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Deng, Shining. "Synthesis of supramolecular architectures using P n -ligands as building blocks." kostenfrei, 2007. http://www.opus-bayern.de/uni-regensburg/volltexte/2008/809/.
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Watson, Alexander. "Avoiding Resolution : Approaches to New P,N Ligands for Asymmetric Catalysis." Thesis, University of Oxford, 2009. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.504647.
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Kelly, Robert David. "Platinum (II) sila-alkyl complexes with N- and P-donor ligands." Thesis, Imperial College London, 1989. http://hdl.handle.net/10044/1/47499.
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Ly, Tuan Q. "New heteroatom ligands and metalla-heterocycles via P-N bond formation." Thesis, Loughborough University, 1997. https://dspace.lboro.ac.uk/2134/32271.
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The reaction of K[N{P(S)Ph2}2] (R = Ph or iPr) with [Mo(N3S2)Cl3] in dichloromethane gives [Mo(N3S2){(ph2(O)PNP(S)P2}2] 1 and [Mo(N3S2){iPr2(O)PNP(S)iPr2}2] 2. X-ray crystallography revealed in both compounds the chelates are co-ordinated to octahedral metal centres. The oxygen atoms are located in the trans position to the nitrogen of the triazene ring. The absence of a chloride counter ion indicates that the metal centre has been reduced from Mo(VI) to Mo(V), and electron paramagnetic resonance spectroscopy confIrmed the reduction of the molybdenum centres. The friction reducing study of compound 1 and [Mo(N3S2)(DTBC)2]Na (DTBC = 3,5–di–tert–butylcatechol) has shown that both compounds exhibit low friction coefficient values.
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Manzi, Lucia. "Preparation and characterisation of rhodium complexes with potentially bidentate P-N and P-O ligands." Thesis, University of Liverpool, 2000. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.366951.
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Cayir, Merve [Verfasser], and Werner R. [Akademischer Betreuer] Thiel. "New N,N,P-Ligands and Their Heterobimetallic Complexes / Merve Cayir. Betreuer: Werner R. Thiel." Kaiserslautern : Technische Universität Kaiserslautern, 2015. http://d-nb.info/1070218774/34.
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Swarts, Andrew John. "Novel transition metal complexes based on N,N and N,P ligands as catalysts for ethylene transformation reactions." Thesis, Stellenbosch : Stellenbosch University, 2014. http://hdl.handle.net/10019.1/86330.
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Artese, Alexandre. "Caractérisation de ligands N,P pour le raffinage de l'uranium(VI) en milieu nitrique." Thesis, Montpellier, 2019. http://www.theses.fr/2019MONTS067.
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Les usines de raffinage des concentrés d’uranium naturel utilisent des procédés hydrométallurgiques pour amener l’uranium à une pureté dite « nucléaire ». Après dissolution dans de l’acide nitrique pour obtenir une solution aqueuse d’uranium(VI), des étapes d’extraction liquide-liquide sont utilisées pour purifier l’uranium. L’extractant phosphate de tri-n-butyle (ou TBP) utilisés lors de ces étapes présente cependant des inconvénients (accumulation de thorium, désextraction non concentrante, solubilité en phase aqueuse non négligeable). L’objectif de l’étude est d’explorer et d’étudier la capacité d’extractants bifonctionels N,P pour l’extraction sélective de l’uranium(VI) en milieu nitrique, et de comprendre les mécanismes entrant en jeu dans l’extraction de l’uranium(VI) ainsi que dans l’extraction de l’élément compétiteur zirconium(IV) par ces extractants.Comme les mécanismes à la base des procédés d'extraction liquide-liquide reposent non seulement sur les propriétés de complexation des molécules extractantes, mais aussi sur leur capacité à former des agrégats supramoléculaires du fait de leur nature amphiphile, les mécanismes d’extraction des ligands bifonctionels N,P ont été étudiés aux échelles moléculaire et supramoléculaire.La compréhension des mécanismes d’extraction a permis d’expliquer la différence de facteur de séparation U/Zr obtenue avec deux extractants amidophosphonates qui ne diffèrent que par la présence d’une chaine centrale alkyle. Il a été montré que cette différence s’explique par la capacité d’un de ces extractants N,P à s’auto-assembler et non par une différence d’affinités des fonctions coordinantesRefining plants of natural uranium concentrates use hydrometallurgical processes to produce uranium with a so-called "nuclear" purity. After dissolution in nitric acid to obtain an aqueous solution of uranium(VI), solvent extraction process is used to purify uranium. The commonly used extractant tri-n-butyl phosphate (or TBP) present however some drawbacks (accumulation of thorium, non-concentrating back-extraction, significant solubility in an aqueous phase).The goal of the study is to explore the ability of new N, P bifunctional extractants for the selective extraction of uranium(VI) in nitric media, and to understand the mechanisms involved in the extraction of uranium(VI) as well as in the extraction of the competing element zirconium(IV).Mechanisms underlying solvent extraction processes being not only based on the chelating properties of the extractant molecules, but also on their capacity to form supramolecular aggregates because of their amphiphilic nature, the extraction mechanisms were studied at both molecular and supramolecular scales.Thanks to the understanding of the extraction mechanisms, the difference of separation factor U/Zr obtained with two amidophosphonates extractants which differ only in the presence of a central alkyl chain could be explained. It was shown that this difference takes its origin in the ability of one of the extractants N, P to self-assemble and not in different affinities of the coordinating functions
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Hand, John Bernard. "Synthesis of novel N, P-ligands and their application in asymmetric catalysis." Thesis, University of Glasgow, 2005. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.428749.
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Radcliffe, James Edward. "Discovery and development of novel P,N ligands for selective ethylene oligomerisation systems." Thesis, Durham University, 2015. http://etheses.dur.ac.uk/11301/.
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This thesis documents the design, discovery, and development of a range of P,N-type ligands and their application in selective ethylene oligomerisation processes. Two classes of ligand have been investigated, PNE (Ph2P(CH2)2NC4H8E, E = NMe, O, CH2) ligands, and iminophosphine ligands (R(PR’2)C=NAr). The coordination chemistry of both these series of compounds has been investigated with various chromium species, and the behaviour of these molecules in ethylene oligomerisation systems probed. Chapter 2 explores the application of PNE ligands to ethylene oligomerisation. The coordination chemistry of the PNE ligands with a selection of group VI starting materials has been investigated. It has been shown that both the PNO and PNC ligands form bidentate complexes upon reaction with CrCl3(THF)3 (e.g. CrCl3(THF)(PNO), 2.1), while attempts to synthesise the PNN analogue proved unsuccessful. The coordination of PNE ligands with Cr(0) and Mo(0) has been studied, with the ligands exhibiting both mono- (e.g. Cr(CO)5(PNN) (2.4) and bi-dentate coordination (e.g. Mo(CO)4(PNN) (2.7)), dependant on the combination of metal and ligand used. Conversion of monodentate Cr(CO)5(κ1-PNN) (2.4) to bidentate Cr(CO)4(κ2-PNN) (2.10) is achieved on reaction with trimethylamine N-oxide. The application of PNE ligands to ethylene oligomerisation systems has been carried out. All of the catalytic systems tested gave primarily polymer products, with no selective ethylene oligomerisation occurring. Chapter 3 describes the development of a modular synthetic route to novel iminophosphine compounds via reaction of imidoyl chlorides with trimethylsilyl phosphines. Using this synthetic process, a library of iminophosphines has been synthesised (3.1-3.26) with varying steric and electronic characteristics. The donor properties of the iminophosphines have been analysed by measurement of ǀ1JSe-Pǀ couplings of the derivative phosphine selenides, with all the compounds demonstrating good phosphine donor properties. Finally, the E/Z isomerisation behaviour of the PCN compounds has been studied, revealing that P-aryl substituted iminophosphines exist as a mixture of the E and Z isomers in equilibrium in solution. Chapter 4 details investigations into the coordination chemistry of iminophosphine ligands with chromium. A selection of ligands have been reacted with CrCl3(THF)3, forming a range of bidentate CrIII(κ2-PCN) complexes (e.g. CrCl3(THF)(Ph(PPh2)C=NPh), 4.1). The coordination of iminophosphine ligands with Cr(0) has shown that the ligands react with Cr(CO)6 to yield both mono- and bi-dentate products (e.g. Cr(CO)4(Ph(PiPr2)C=N(2,6-iPr2C6H3)) (4.7) and Cr(CO)5(Ph(PiPr2)C=N(2,6-iPr2C6H3)) (4.8), respectively). The denticity of these Cr(CO)(6-n)(κn-PCN) complexes can be controlled through the removal and addition of CO in the atmosphere. Chapter 5 recounts the use of the novel iminophosphines as ligands in selective ethylene oligomerisation systems. A wide range of catalytic conditions were tested, including varying the chromium source, solvent, reaction temperature and pressure, the use of polymer reducing additives, and the dosing of O2 into the reaction. It has been shown that a catalytic process using Cr(2-EH)3, 1 equivalent of iminophosphine 3.9, 49 bar C2H4, in methylcyclohexane at 60 °C, with 0.66 ppm O2 and 100 equivalents of ZnEt2 yields a highly active and selective ethylene tri-/tetramerisation process.
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Niaz, Basit [Verfasser]. "Synthesis of Novel Biaryl-Type P=C-N-Heterocyclic σ2P,N- and σ2P,σ3P-Hybrid Ligands / Basit Niaz." Greifswald : Universitätsbibliothek Greifswald, 2012. http://d-nb.info/1021299014/34.
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Dugal-Tessier, Julien. "Synthesis of P,N-chelate phosphaalkene–oxazoline ligands and their applications in asymmetric catalysis." Thesis, University of British Columbia, 2010. http://hdl.handle.net/2429/31408.
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This thesis outlines the design, synthesis and utilization of phosphaalkene-based ligands
for asymmetric catalysis.
Transition metal catalysis studies that utilize achiral phosphaalkene-based ligands are
reviewed in Chapter 1. In addition, the synthesis and reactivity of phosphaalkenes are briefly
introduced in this chapter.
The reactivity of a palladium(II) phosphaalkene complex [MesP=CPh(2-py)⋅PdCl₂]
bearing the smaller P-Mes substituent compared to the traditional Mes* is described in Chapter
2. This complex was found to be a competent catalyst for the Overman–Claisen rearrangement
with yields ranging from 33% to 91%.
In Chapter 3, a modular route to a set of chiral phosphaalkene–oxazoline [PhAk–Ox,
R′P=CR′′(C(i-Pr-Ox)R₂)] proligands is described. The synthetic route starts from a chiral pool
material (L-valine) and generates the P=C bond by a phospha-Peterson reaction. The electronic
and steric properties of the proligands (R′, R′′ and R) were modified using this synthetic route.
MesP=CPh(C(i-Pr-Ox)Me₂) was thermally polymerized to generate poly(methylenephosphine).
The investigation of the coordination chemistry of PhAk–Ox proligands is described in
Chapter 4. Rhodium(I) and iridium(I) PhAk–Ox complexes were characterized by X-ray
crystallography and NMR spectroscopy. Rhodium(I) PhAk–Ox complexes were found to be
active in the asymmetric allylic alkylation of ethyl (1-phenylallyl) carbonate with dimethyl
malonate as a nucleophile. The optimal conditions generated products in 37% yield and 66% ee.
The investigations of PhAk–Ox ligands in palladium(0) catalyzed allylic alkylation of
1,3-diphenylpropenyl acetate using malonate type nucleophiles are reported in Chapter 5. The
structural modification of the ligand through the incorporation of a gem-dimethyl group [MesP=CPh(C(4-i-Pr-5-Me₂-Ox)Me₂)] was needed to optimize yields (73–95%) and
enantioselectivities (79–92%). Ring-closing metathesis processes were used to generate
enantioenriched carbocycles.
To conclude, the results presented in this dissertation represent the highest reported
enantioselectivities for a reaction utilizing a phosphaalkene-based ligand. These results also
serve as a proof of concept that phosphaalkene ligands can be used in asymmetric catalysis.
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Camus, Jean-Michel. "Synthèse, chimie de coordination et catalyse avec des ligands bifonctionnels chiraux de type P,N." Dijon, 2002. http://www.theses.fr/2002DIJOS034.
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Agostinho, Magno. "Nouveaux ligands de type N,O et P,N et leurs applications en chimie de coordination et catalyse homogène." Université Louis Pasteur (Strasbourg) (1971-2008), 2006. https://publication-theses.unistra.fr/public/theses_doctorat/2006/AGOSTINHO_Magno_2006.pdf.
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Nous avons synthétisé des ligands zwitterioniques N,O benzoquinonemonoimine N-substitués qui possèdent 6π+6π électrons (molécules potentiellement antiaromatiques). Ces ligands ont été préparés par une nouvelle procédure, très efficace, basée sur les premières réactions de transamination en chimie des quinones. Les ligands tridentates réagissent à température ambiante avec [Ni(acac)2] dans un rapport molaire ligand/métal de 2:1 pour former des complexes octaédriques de nickel. Ces complexes ont été testés en catalyse d'oligomérisation de l'éthylène avec MAO et AlEtCl2 comme cocatalyseurs. L'un des atouts majeurs de ces complexes est la possibilité de faire varier la nature et l'encombrement stérique des substituants portés par les atomes d'azote afin d'orienter la sélectivité du catalyseur vers des chaînes oligomériques de longueur variable. Nous avons trouvé des valeurs de fréquence de rotation allant jusqu’a 48 200 mol C2H4/(mol Ni)h, en présence de seulement 10 équivalents de AlEtCl2. Les sélectivités en dimères de l’éthylène ont atteint 94%, en présence de 100 equiv of MAO. Des ligands P,N phosphino-oxazoline, phosphinito-oxazoline et phosphonite-oxazoline ont été préparés. Ces ligands réagissent avec [PdClMe(COD)] (COD = cyclooctadiène) pour former des complexes de type [PdClMe(P,N)], à partir desquels les complexes de type [Pd(CF3SO3)Me(P,N)] ont été préparés par abstraction de chlorure avec AgCF3SO3. Par insertion de monoxyde de carbone puis de l’éthylène ou de l’acrylate de méthyle dans la liaison Pd-C des complexes [Pd(CF3SO3)Me(P,N)] les dérivés alkyles [Pd{CHRCH2C(O)Me}(P,N)]CF3SO3 (R = H ou CO2Me) ont été isolés et caractérisés spectroscopiquement. De nombreux produits d’insertion ont été complètement caractérisés par diffraction des rayons X et leurs structures représentent des exemples encore rares de produits d’insertion CO/éthylène et CO/acrylate de méthyle aussi complètement caractérisésThe zwitterionic N,N’-dialkyl-2-amino-5-alcoholate-1,4-benzoquinonemonoiminium derivatives were obtained from 4,6-diaminoresorcinol by a transamination reaction. These tridentate ligands react with [Ni(acac)2] to form the corresponding octahedral Ni(II) 2:1 complexes. These complexes were tested in catalytic ethylene oligomerization with MAO and AlEtCl2 as cocatalysts. The turnover frequencies were up to 48 200 mol of C2H4/(mol of Ni) h, in the presence of only 10 equiv of AlEtCl2. Selectivities for ethylene dimers were up to 94%, in the presence of 100 equiv of MAOPhosphine-oxazoline, phosphinite-oxazoline and phosphonite-oxazoline P,N-type ligands were prepared. These ligands react with [PdClMe(COD)] (COD = cyclooctadiene) to give complexes of the type [PdClMe(P,N)], which led to [Pd(CF3SO3)Me(P,N)] by AgCF3SO3-promoted chloride abstraction. The alkyl ketone chelate complexes [Pd{CHRCH2C(O)Me}(P,N)]CF3SO3 (R = H or CO2Me) have been isolated from the stepwise insertion reaction of CO and ethylene or methyl acrylate into the Pd-C bond of complexes [Pd(CF3SO3)Me(P,N)], and spectroscopically characterized. Many insertion products have been fully characterized by X-ray difraction and their structures represent still rare examples of structurally characterized CO/ethylene and CO/methyl acrylate coupling products
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Agostinho, Magno Braunstein Pierre. "Nouveaux ligands de type N,O et P,N et leurs applications en chimie de coordination et catalyse homogène." Strasbourg : Université Louis Pasteur, 2007. http://eprints-scd-ulp.u-strasbg.fr:8080/667/01/Manuscrit_06-Dec.pdf.
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Dwadnia, Nejib. "Ligands ferrocéniqes hybrides (P, N) : synthèse, coordination aux métaux et applications en catalyse de couplage d'arylation." Thesis, Bourgogne Franche-Comté, 2017. http://www.theses.fr/2017UBFCK050/document.
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La thématique de recherche développée au cours de cette thèse concerne l’élaboration de nouveaux ligands mixtes ferrocéniques hybrides-(P,N) à conformation contrôlée, robustes et stables à l’air. Ces ligands tétradentes hybrides comportent deux types de fonctions coordinnantes aux propriétés stériques et électroniques distinctes. Leur chimie de coordination avec des métaux tels que l’or ou le palladium a été étudiée et certains complexes d’Au(I) isolés ont été utilisés en catalyse de couplage d’arylation des iodures d’aryles. La première partie de cette thèse porte sur une étude bibliographique concise reflétant la diversité des ligands ferrocénique azotés et hybride-(P,N) et leurs voies de synthèse, pour finalement retracer leur chimie de coordination aux métaux de transition (Pd, Au) ainsi que leurs applications catalytiques. La deuxième partie traite la synthèse d’une famille de composés bis(aminométhyl)-ferrocène et les dérivés associés de manière sélective par amination réductrice du 1,1'- diformylferrocène ou du 1,1'-bis(tert-butyl)-3,3'-diformylferrocène avec une variété d’amines primaires et secondaires. Dans la troisième partie nous présentons les stratégies de synthèse qui ont été utilisées pour la préparation de hybrides-(P,N) ferrocéniques ainsi que leur contrôle conformationnel, et la caractérisation structurale de ces molécules. Leur coordination à des sels de palladium a été étudiée. Les complexes de coordinations correspondants ont étés isolés avec de très bons rendements, et caractérisés en solution par RMN 1H , 13C, 31P, 15N, et à l’état solide par diffraction des rayons X. La quatrième et dernière partie est dédiée à l’étude de la coordination à l’or. Trois nouveaux complexes d’Au(I) dinucléaires, incorporant des ligands ferrocéniques hybride-(P,N), ont étés isolés est caractérisés. L‘un parmi ces complexes a montré une efficacité particulière pour la réaction d’arylation des iodures d’arylesThe research theme developed during this thesis concerns the development of new hybrid ferrocene hybrid (P, N) ligands with controlled conformation, robust and stable to air. These hybrid tetradent ligands comprise two types of coordinating functions with distinct steric and electronic properties. Their coordination chemistry with metals such as gold or palladium has been studied and some isolated Au (I) complexes have been used in the arylation coupling catalysis of aryl iodides
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Brück, Andreas. "Multidentate P, N-ligands in the synthesis, characterisation and application of homo- and heterobimetallic complexes /." München : Verl. Dr. Hut, 2009. http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&doc_number=017660628&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA.
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Kuznetsov, Vladimir F. "Synthesis, structure and reactivity of transition metal complexes containing P-, O- and N-donor ligands." Thesis, National Library of Canada = Bibliothèque nationale du Canada, 2001. http://www.collectionscanada.ca/obj/s4/f2/dsk3/ftp05/NQ66161.pdf.
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Delapierre, Guillaume. "Des ligands chiraux de type P, N : les quinoléines-phosphines. Synthèse et applications en catalyse asymétrique." Aix-Marseille 3, 2001. http://www.theses.fr/2001AIX30072.
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Dix-sept nouveaux composés chiraux de type pyridine- et quinoléine-phosphines ont été synthétisés. Ils possèdent pour la plupart un atome de phosphore chiral et ont été utilisés en tant que ligands de métaux de transition. En se basant sur la structure du QUIPHOS, plusieurs modifications ont ainsi été apportées, notamment par la variation de l'auxiliaire chiral et par la substitution du cycle quinoléine en ortho et para de l'atome d'azote. Ces ligands ont été appliqués en substitution nucléophile allylique catalysée par le palladium et leur efficacité a été comparée à celle du QUIPHOS. En alkylation et en amination allyliques, les excès énantiomériques atteignent respectivement 78 et 93 %. Les résultats précédemment obtenus avec le QUIPHOS n'ont pas été améliorés, respectivement 85 et 93 %, mais nous avons démontré que le remplacement de la (S)-2-anilinomthylpyrrolidine par un autre auxiliaire chiral provoquait une forte baisse de l' énantiosélectivité. Une étude de la régiosélectivité de cette réaction a mis en évidence une régiosélectivité totale ne faveur du produit linéaire. En utilisant le QUIPHOS comme ligand, nous avons optimisé les conditions expérimentales de la réaction d'addition conjuguée du diéthylzinc sur la cyclohexen-2-one. .Seventeen new quinoline- and pyridine-phosphine compounds were synthesised. Most of them have a chiral phosphorus atom and were used as ligands of transition metals in asymmetric catalysis. From the first ligand we synthesised, the QUIPHOS, we brought several modifications. Mainly, we changed the nature of the chiral auxiliary and we substituted the quinoline ring in ortho and para positions. We applied these compounds as ligands in allylic alkylation and allylic amination. We obtained good ennatiomeric excesses, respectively 78 and 93 %. We didn't improve the first results obtained with QUIPHOS, respectively 85 an 93 % but we showed that the enantiomeric excess strongly decreases when replacing the (S)-anilinomthylpyrrolidine by another chiral auxiliary. The regioselectivity of the reaction was studied with QUIPHOS too. We observed a total regioselectivity in favour of the non chiral linear product in allylic alkylation. .
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Biosca, Brull Maria. "Fitting the catalysts for effective enantioselective C-X bond forming reactions. Theoretically guided ligand design and mechanistic investigations." Doctoral thesis, Universitat Rovira i Virgili, 2018. http://hdl.handle.net/10803/665121.
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La creixent demanda de compostos enantiomèricament purs, ha incrementat l’interès pel desenvolupament de metodologies per l’obtenció d'aquests compostos. Entre elles, la catàlisi asimètrica és la tècnica més emprada. En aquesta metodologia, l'elecció lligand quiral és clau per l'obtenció de elevades activitats i enantioselectivitats. En aquest context, aquesta tesis és centra en la síntesis de diferents famílies de lligands quirals altament modulars a partir de productes de partida d'elevada disponibilitat. Més concretament, s’han sintetitzat diverses famílies de lligands heterodadors P-oxazolina (P= fosfina, fosfinit, fosfit, fosforamidit), P-altres grups N-dadors (P= fosfit, fosforamidit, fosfonit i N= tiazol, sulfoximina, hidrazona, amina, piridina), P-tioèter (P= fosfina, fosfinit, fosfit) i una família de lligands fosfina quiral-fosfit. Aquests lligands s'han aplicat en la reacció d’hidrogenació d’olefines funcionalitzades i mínimament funcionalitzades catalitzada per Rh i Ir, la reacció de substitució al·lílica i la reacció de protonació descarboxilativa d’oxindoles ambdues catalitzades per Pd. A més a més, en alguns casos, s'han dut a terme estudis computacionals en combinació amb assajos experimentals per estudiar l'origen de les enantioselectivitats obtingudes o bé per guiar l'optimització dels lligand.La creciente demanda de compuestos enantioméricamente puros, ha incrementado el interés por el desarrollo de metodologías para la obtención de dichos compuestos. Entre ellas, la catálisis asimétrica es la técnica mas utilizada. En dicha metodología, la elección del ligando quiral es clave para la obtención de elevada actividades i enantioselectividades. En este contexto, esta tesis se centra en la síntesis de diferentes familias de ligandos quirales altamente modulares a partir de productos de partida de elevada disponibilidad. Más concretamente, se ha trabajado en la síntesis de ligandos heterodadores P-oxazoline (P= fosfina, fosfinito, fosfito, fosforamidito), P-otros grupos N-dadores (P= fosfito, fosforamidito, fosfonito y N= tiazol, sulfoximina, hidrazona, amina, piridina), P-tioéter (P= fosfina, fosfinito, fosfito) i una familia de ligandos fosfina quiral-fosfito. Estos ligandos se han aplicado en la reacción de hidrogenación de olefinas funcionalitzadas i mínimamente funcionalitzadas catalizada por Rh i Ir, la reacción de substitución alílica y la reacción de protonación descarboxilativa de oxindolas ambas catalizadas por Pd. Además, en algunos casos, se han realizado cálculos computacionales en combinación con ensayos experimentales para estudiar el origen de las enantioselectividades obtenidas o bien para guiar la optimización de los ligandos.
The growing demand on enantiomerically pure compounds has stimulated the interest for the development of methodologies to obtain these compounds. Among them, asymmetric catalysis is one of the most employed tools. In this technic, the choice of the chiral ligand is fundamental to obtain high levels of activity and enantioselectivity. In this context, this thesis is focused on the synthesis of several families of highly modular chiral ligands from readily available starting materials. Particularly, we worked on the synthesis of P-oxazoline (P= phosphine, phosphinite, phosphite, phosphoroamidite), P-other N-donor groups (P= phosphite, phosphoroamidite, phosphonite and N= thiazole, sulfoximine, hydrazone, amine, pyridine), P-thioether (P= phosphine, phosphinite, phosphite) and a family of P*-stereogenic phosphine-phosphite ligands. These ligands have been applied in the Rh- and Ir-catalyzed hydrogenation of functionalized and minimally functionalized olefins, Pd-catalyzed allylic substitution reaction and Pd-catalyzed decarboxylative protonation. Furthermore, in some cases, DFT studies in combination with experimental ones have been performed to better understand the origin of the obtained enantioselectivities or in order to guide the ligand optimization.
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Leca, François. "Nouveaux ligands P, N à motifs phosphole et 2-phospholène : synthèse, coordination et applications pour la catalyse." Rennes 1, 2004. http://www.theses.fr/2004REN10047.
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L'intérêt porté aux ligands phosphoré en catalyse a connu un essor remarquable depuis le milieu des années 1980. L'étude bibliographique de ce manuscrit détaille quelques exemples de catalyseurs possédant des ligands hétérocycliques phosphorés. Une première partie décrit la chimie de coordination et la réactivité vis à vis de l'éthylène de ligands P,N 2-pyridylphospholes. La seconde partie de ce travail reporte la synthèse d'une nouvelle famille de ligands P,N chiraux sur le phosphore : les 2-pyridyl-2-phospholènes. L'application en substitution allylique et en télomérisation de diènes a été effectuée.
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Sutaria, Adil Dinyar. "The effect of heterodentate chelating P-N ligands on allyl and alkyl complexes of palladium and platinum." Thesis, University of Salford, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.308256.
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Coetzee, Jacorien. "New developments in the coordination chemistry of gold(1), gold(II) and gold(III) with C-, N-, P-and S-Donor ligands /." Link to the online version, 2007. http://hdl.handle.net/10019/412.
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Vuong, Khuong Quoc Chemistry Faculty of Science UNSW. "Metal complex catalysed C-X (X = S, O and N) bond formation." Awarded by:University of New South Wales. Chemistry, 2006. http://handle.unsw.edu.au/1959.4/23015.
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This thesis describes the catalysed addition of X-H bonds (X = S, O and N) to alkynes using a range of novel rhodium(I) and iridium(I) complexes containing hybrid bidentate phosphine-pyrazolyl, phosphine-imidazolyl and phosphine-N heterocyclic carbene (NHC) donor ligands. The synthesis of novel bidentate phosphine-pyrazolyl, phosphine-imidazolyl (P-N) and phosphine-NHC (PC) donor ligands and their cationic and neutral rhodium(I) and iridium(I) complexes [M(P N)(COD)]BPh4, [M(PC)(COD)]BPh4, [Ir(P-N)(CO)2]BPh4 and [M(P-N)(CO)Cl] were successfully performed. An unusual five coordinate iridium complex with phosphine-NHC ligands [Ir(PC)(COD)(CO)]BPh4 was also obtained. Seventeen single crystal X-ray structures of these new complexes were determined. A range of these novel rhodium and iridium complexes were effective as catalysts for the addition of thiophenol to a variety of alkynes. Iridium complexes were more effective than rhodium analogues. Cationic complexes were more effective than neutral complexes. Complexes with hybrid phosphine-nitrogen donor were more effective than complexes containing bidentate nitrogen donor ligands. An atom-economical, efficient method for the synthesis of cyclic acetals and bicyclic O,O-acetals was successfully developed based on the catalysed hydroalkoxylation. Readily prepared terminal and non-terminal alkyne diols were cyclised into bicyclic O,O-acetals in quantitative conversions in most cases. The efficiency of a range of rhodium and iridium complexes containing bidentate P-N and PC donor ligands as catalysts for the cyclisation of 4-pentyn-1-amine to 2-methyl-1-pyrroline varied significantly. The cationic iridium complexes with the bidentate phosphine-pyrazolyl ligands, [Ir(R2PyP)(COD)]BPh4 (2.39-2.42) were extremely efficient as catalysts for this transformation. Increasing the size of the substituent on or adjacent to the donor led to improvement in catalytic activity of the corresponding metal complexes. The mechanism of the catalysed hydroalkoxylation was proposed to proceed by the initial activation of the alkyne via ?? coordination to the metal centre. The ?? binding of both aliphatic and aromatic alkynes to [Ir(PyP)(CO)2]BPh4 (2.44) was observed by low temperature NMR and no reaction between 2.44 and alcohols was observed. In contrast, the facility in which thiol and amine oxidatively added to 2.44 led the proposal that in the hydrothiolation and hydroamination reaction, the catalytic cycle commences with the activation of the X-H bond (X = S, N) by an oxidative addition process.
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Bertrand-Caumont, Karine. "Conception et synthèse de N. C. E. (New Chemical Entities), ligands des récepteurs NK1 de la substance P." Lille 1, 1996. https://pepite-depot.univ-lille.fr/LIBRE/Th_Num/1996/50376-1996-262-1.pdf.
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Depuis quelques années, d'importants efforts ont été réalisés pour élaborer des antagonistes des récepteurs nk1 de la substance p (sp). Nous détaillons ici la mise en évidence de ligands de ces macromolécules. Une étude s'appuyant sur les mécanismes de reconnaissance moléculaire d'antagonistes connus et sur la confrontation de relations structure-affinité établies pour des molécules structuralement voisines révèle l'existence de deux types de pharmacophores. Ils se distinguent par la substitution du groupement benzylique qu'ils portent : le pharmacophore de type i possède un groupement benzylique monosubstitué en ortho par un méthoxy, voire non substitué le pharmacophore de type ii est caracterisé par un groupement benzylique disubstitué en méta par des trifluorométhyles. Des modifications structurales de leads peptidiques, identifies pour les deux classes de ligands, permettent d'élaborer des n. C. E. (new chemical entities) ligands des récepteurs de la sp. Possédant les pharmacons de type i, trois squelettes révèlent une liaison modeste pour la protéine nk1. Ils s'articulent autour d'un noyau indole pour le premier. D'un noyau 1,2,3,4-tétrahydroquinoxaline pour le deuxième. D'une pipérazine pour le dernier. Une autre structure originale fondée sur le noyau 1-amino-1,2,3,4-tétrahydronaphtalène contient les pharmacogroupements de type ii et révèle une affinité intéressante pour les récepteurs de la sp
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Ganić, Adnan [Verfasser]. "Iridium-Catalyzed Asymmetric Hydrogenation: Development of New N,P Ligands and Hydrogenation of Alkenyl Boronic Esters / Adnan Ganić." München : Verlag Dr. Hut, 2013. http://d-nb.info/1034003240/34.
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Thibault, Marie-Hélène. "Design et synthèse de ligands hexadentates hybrides P, N et S, N : étude de leur chimie de coordination avec des métaux de transition et du groupe pricipal." Thesis, Université Laval, 2010. http://www.theses.ulaval.ca/2010/26586/26586.pdf.
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Lemouzy, Sébastien. "Synthèse stéréospécifique et chimie de coordination de ligands hétérobifonctionnels P-stéréogènes : vers le développement de méthodologies de couplages C-C palladocatalysés." Thesis, Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4359.
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La première partie de ce manuscrit traite de la synthèse de phosphine-boranes P-stéréogènes énantioenrichis à partir d’un précurseur développé par notre laboratoire : le H-phénylphosphinate d’adamantyle. Grâce au développement d’une séquence monotope, une variété d’oxydes de phosphine P-stéréogènes de haute pureté optique a pu être synthétisée. Ces composés comportant une attache hydroxyle ont ensuite été réduits de façon stéréospécifique en présence de borane pour générer les précurseurs phosphine-boranes correspondants. Lors de cette étape de réduction, l’importance de la fonction hydroxyle a été mise en évidence, et un mécanisme basé sur la formation d’une espèce phosphaboracyclique intermédiaire a été proposé, sur la base de l’isolement d’intermédiaires réactionnels O-borés. Les trois rôles du borane (activation, réduction, protection de la phosphine) ont été clairement identifiés dans ce processus. Dans un second temps, nous avons pu mettre à profit la rétroaddition du groupement hydroxyalkyle en milieu basique lors de l’alkylation stéréospécifique chimiodivergente de phosphure-boranes masqués. Cette rétroaddition a permis de contourner l’instabilité chimique et configurationnelle des phosphures générés in situ, permettant l’accès à des phosphine-boranes fonctionnalisés de manière énantiospécifique. Ces ligands P,N ont été ensuite complexés au palladium et les complexes ont pu être testés comme catalyseurs de couplages C-C énantiosélectifs. Lors de ces couplages, l’angle de morsure du ligand s’est révélé crucial pour la réactivité du système catalytiqueThe first part of this manuscript deals with the synthesis of enantioenriched P-stereogenic phosphine-boranes from a chiral precursor developed in our laboratory: H-adamantyl phenylphosphinate. Through the design of a one-pot procedure, the synthesis of a wide array of highly enantioenriched phosphine oxides has been achieved. These hydroxy-functionalised compounds were reduced stereospecifically under borane conditions to yield the corresponding hydroxyalkylphosphine-boranes. During the study of this reaction, the importance of hydroxy group has been highlighted, and a mechanism relying on the formation of transient phosphaboracyclic intermediate could be proposed, on the basis of kinetic observation and isolation of O-borylated intermediates. In this transformation, borane seems to display three roles: activating, reducing and protecting agent. Next, we were able to take advantage of the retroaddition of hydroxyalkyl moiety under basic conditions to develop a new approach for the stereospecific and chemodivergent alkylation of masked secondary phosphine-boranes. This unusual reactivity allowed us to circumvent the relative chemical and configurational instability of such in situ generated phosphido-boranes intermediate, thus enabling the stereospecific synthesis of functionalised tertiary phosphine-boranes. These P-N ligands have been complexed to palladium, and the catalytic activity of these complexes in enantioselective C-C couplings has been studied. During the catalytic process, it appears that the ligand bite angle plays an important role in the catalyst activity
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Lemouzy, Sébastien. "Synthèse stéréospécifique et chimie de coordination de ligands hétérobifonctionnels P-stéréogènes : vers le développement de méthodologies de couplages C-C palladocatalysés." Electronic Thesis or Diss., Aix-Marseille, 2016. http://www.theses.fr/2016AIXM4359.
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La première partie de ce manuscrit traite de la synthèse de phosphine-boranes P-stéréogènes énantioenrichis à partir d’un précurseur développé par notre laboratoire : le H-phénylphosphinate d’adamantyle. Grâce au développement d’une séquence monotope, une variété d’oxydes de phosphine P-stéréogènes de haute pureté optique a pu être synthétisée. Ces composés comportant une attache hydroxyle ont ensuite été réduits de façon stéréospécifique en présence de borane pour générer les précurseurs phosphine-boranes correspondants. Lors de cette étape de réduction, l’importance de la fonction hydroxyle a été mise en évidence, et un mécanisme basé sur la formation d’une espèce phosphaboracyclique intermédiaire a été proposé, sur la base de l’isolement d’intermédiaires réactionnels O-borés. Les trois rôles du borane (activation, réduction, protection de la phosphine) ont été clairement identifiés dans ce processus. Dans un second temps, nous avons pu mettre à profit la rétroaddition du groupement hydroxyalkyle en milieu basique lors de l’alkylation stéréospécifique chimiodivergente de phosphure-boranes masqués. Cette rétroaddition a permis de contourner l’instabilité chimique et configurationnelle des phosphures générés in situ, permettant l’accès à des phosphine-boranes fonctionnalisés de manière énantiospécifique. Ces ligands P,N ont été ensuite complexés au palladium et les complexes ont pu être testés comme catalyseurs de couplages C-C énantiosélectifs. Lors de ces couplages, l’angle de morsure du ligand s’est révélé crucial pour la réactivité du système catalytiqueThe first part of this manuscript deals with the synthesis of enantioenriched P-stereogenic phosphine-boranes from a chiral precursor developed in our laboratory: H-adamantyl phenylphosphinate. Through the design of a one-pot procedure, the synthesis of a wide array of highly enantioenriched phosphine oxides has been achieved. These hydroxy-functionalised compounds were reduced stereospecifically under borane conditions to yield the corresponding hydroxyalkylphosphine-boranes. During the study of this reaction, the importance of hydroxy group has been highlighted, and a mechanism relying on the formation of transient phosphaboracyclic intermediate could be proposed, on the basis of kinetic observation and isolation of O-borylated intermediates. In this transformation, borane seems to display three roles: activating, reducing and protecting agent. Next, we were able to take advantage of the retroaddition of hydroxyalkyl moiety under basic conditions to develop a new approach for the stereospecific and chemodivergent alkylation of masked secondary phosphine-boranes. This unusual reactivity allowed us to circumvent the relative chemical and configurational instability of such in situ generated phosphido-boranes intermediate, thus enabling the stereospecific synthesis of functionalised tertiary phosphine-boranes. These P-N ligands have been complexed to palladium, and the catalytic activity of these complexes in enantioselective C-C couplings has been studied. During the catalytic process, it appears that the ligand bite angle plays an important role in the catalyst activity
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Rahm, Fredrik. "Chiral Pyridine-Containing Ligands for Asymmetric Catalysis. Synthesis and Applications." Doctoral thesis, KTH, Chemistry, 2003. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-3564.
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This thesis deals with the design and syntheses of chiral,enantiopure pyridinecontaining ligands and their applicationsin asymmetric catalyis.
Chiral pyridyl pyrrolidine ligands and pyridyl oxazolineligands were synthesized and employed in thepalladium-catalysed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with dimethyl malonate. Theinfluence of the steric properties of the ligands wereinvestigated.
Ditopic ligands, containing crown ether units as structuralelements, were synthesized and some of the ligands were used asligands in the palladiumcatalysed allylic alkylation of1,3-diphenyl-2-propenyl acetate with dimethyl malonate. A smallrate enhancement was observed, compared with analogous ligandslacking the crown ether unit, when these ditopic ligands wereused in dilute systems.
A modular approach was used to synthesize chiralenantiomerically pure pyridyl alcohols and C2-symmetric2,2-bipyridines, with the chirality originating from thechiral pool. Electronic and steric properties of the compoundswere varied and they were used as ligands in theenantioselective addition of diethylzinc to benzaldehyde. Thesense of asymmetric induction was found to be determined by theabsolute configuration of the carbinol carbon atom. Theelectronic properties of the ligands had a minor influence onthe levels of enantioselectivity induced by the ligands.
Chiral pyridyl phosphinite ligands and pyridyl phosphiteligands were synthesized from the pyridyl alcohols andevaluated as ligands in palladiumcatalysed allylic alkylations.With the phosphinite ligands, the sense of chiral induction wasfound to be determined by the absolute configuration of theformer carbinol carbon atom. A kinetic resolution of theracemic starting material was observed with one of thephosphite ligands. Moderate enantioselectivities wereachieved.
Kewords:asymmetric catalysis, chiral ligand, chiralpool, oxazoline, crownether, ditopic receptor, bipyridine,pyridyl alcohol, modular approach, P,Nligand, diethylzinc,allylic alkylation.
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Coetzee, Jacorien. "New developments in the coordination chemistry of Gold(I), Gold(II) and Gold(III) with C-, N- , P-and S-donor ligands." Thesis, Stellenbosch : University of Stellenbosch, 2007. http://hdl.handle.net/10019.1/1702.
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Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2007.A comprehensive, comparative structural study of gold(I), gold(II) and gold(III) compounds with the general formula [Aux(C6F5)y(tht)z] (tht = tetrahydrothiophene) was performed. The series of compounds included the unprecedented dinucleur gold(II) compound, tetrakis(pentafluorophenyl)bis(tetrahydrothiophene)digold(II), which could be prepared in a rational manner. This very unique compound represents the first example of an unbridged dinucleur gold(II) compound in which the gold(II) centres are not stabilised by chelating ligands. Formation of this compound was postulated to have taken place by radical pentafluorophenyl (pfp) ligand migration along with AuII–AuII bond formation. It may therefore be regarded as a rare example of labile behaviour by a generally inert pfp ligand. In addition to this compound, the crystal and molecular structures of the wellknown gold(I) and gold(III) precursor compounds, (pentafluorophenyl)(tetrahydrothiophene) gold(I) and tris(pentafluorophenyl)(tetrahydrothiophene)gold(III) were carried out and are described for the first time. The latter underwent a unique mononuclear ligand rearrangement (metathesis or disproportionation) reaction in solution to yield the novel rearrangement product, bis(pentafluorophenyl)bis(tetrahydrothiophene)gold(III)tetrakis- (pentafluorophenyl)gold(III). In all the complexes, the Au–C and Au–S bond lengths displayed a variation which appears to be dependent on the oxidation state of the central gold atom. Both of these bond types were found to descrease in the order Au(II) > Au(III) > Au(I)...
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Allouch, Fatima. "Synthèse et applications de nouveaux complexes métallocéniques multidentes." Thesis, Dijon, 2013. http://www.theses.fr/2013DIJOS002.
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Ce mémoire porte sur l’accès simple et peu coûteux à de nouveaux ligands ferrocéniques aminés et aminophosphinés et leur coordination avec des métaux de transition pour des applications en catalyse homogène.Des métallo-ligands aminés flexibles ont été obtenus et caractérisés après amination réductrice du 1,1’-diformylferrocène. D’autres ligands (N,N) rigides ont été isolés au départ du précurseur du 1,1’-di-tert-butyl-3,3’-diformylferrocène. Des aza-ferrocénophanes ont également été facilement préparés avec ces deux précurseurs carbonylés. Lors de la coordination de ces ligands avec le palladium, un palladacycle original a été isolé et caractérisé par diffraction de rayons X.Des ligands ferrocéniques (N,P) ont été obtenus par trois méthodes: i) ortholithiation de ligands ferrocéniques aminés suivie d’un ajout de chlorophosphine, ii) amination réductrice des ferrocènes formylés substitués ou non en présence d’amine portant une fonction phosphine, iii) substitution directe du ferrocène dilithié par des chlorophosphines comportant un hétérocycle azoté. Leur coordination avec du palladium et du platine a été étudiée. Ces métallo-ligands hybrides ont été impliqués dans des réactions de chlorures d’aryle avec des acides arylboroniques (couplage de Suzuki), ainsi que dans la réaction de Sonogashira avec le couplage de bromures et de chlorures d’aryle avec le phénylacétylèneThis thesis focuses on simple and inexpensive access to new amino and aminophosphine ferrocenyl ligands and their coordination with transition metals for applications in homogeneous catalysis.Flexible amine metallo-ligands were obtained and characterized after reductive amination of 1,1'-diformylferrocene. Other rigid (N,N) ligands were isolated starting from the precursor 1,1'-di-tert-butyl-3, 3'-diformylferrocene. Aza-ferrocenophanes were also easily prepared with these two formyl precursors. During the coordination of these ligands with palladium, a stable and original palladacycle was isolated and characterized by DRX.(N,P) ferrocenyl ligands were obtained by three methods: i) ortholithiation of aminoferrocenyl ligands followed by addition of chlorophosphines, ii) reductive amination of substituted or not formylferrocene in the presence of amine bearing a phosphine function, iii) direct substitution of dilithiated ferrocene by chlorophosphines with a nitrogen-containing heterocycle. Their coordination with palladium and platinum has been studied. These hybrid metallo-ligands have been implicated in the reactions of aryl chlorides to arylboronic acids (Suzuki cross-coupling), as well as in the Sonogashira reaction involving of coupling aryl bromides and chlorides to phenylacetylene
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Sala, Román Xavier. "New Ruthenium complexes containing N, P and S-donor type of ligands: coordination chemistry, characterization and application to asymetric and non-asymetric catalysis." Doctoral thesis, Universitat de Girona, 2007. http://hdl.handle.net/10803/8043.
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Síntesi de nous complexos de Ruteni amb lligands no quirals que tenen per fórmula [Ru(phen)([9]aneS3)X] (on X = H2O, py i MeCN). Caracterització espectroscòpica electroquímica i estructural d'aquesta família de complexos. Estudi de les seves propietats catalítiques en front a l'oxidació de substrats orgànics com l'alcohol benzílic en reaccions d'electrocatàlisi. Avaluació cinètica dels mecanismes de substitució entre els complexos Ru-py i Ru-MeCN. Generació d'un interruptor molecular foto-induït.Síntesi de nous complexos quirals de Ru atropoisomèricament purs amb lligands oxazolínics que tenen per fórmula [Ru(trpy)(Ph-box-R)X] on (X = Cl, H2O, py, MeCN, 2-OH-py). Caracterització estructural exhaustiva en estat sòlid (Raig-X) en solució (RMN) i en fase gas (càlculs DFT). Avaluació de la seva activitat catalítica en reaccions asimmetriques d'epoxidació de substrats proquirals.
Síntesi de nous lligands polipiridílics quirals amb simetria C3. Estudi de la seva química de coordinació i avaluació de la seva activitat catalítica en reaccions asimmetriques d'oxidació i reducció.
Synthesis, spectroscopic characterization and redox properties of a new Ru-H2O complex containing 1,10-phenantroline and the soft [9]aneS3 ligand. Substitution pathways of a new Ru-py complex [Ru(phen)(py)([9]aneS3)]2+ to form the corresponding Ru-MeCN complex through kinetic analysis. Kinetic establishment of a reaction intermediate. Synthesis of new Ru(II) complexes containing the chiral 1,2-bis(oxazolinyl) benzene ligand. Rotationally restricted isomers were produced upon coordination to a ruthenium metal centre. Atropisomeric discrimination was observed due to steric effects between the oxazolinic and the auxiliary ligands. Evaluacion of the catalytic activity of the family of complexes in C=C double bond epoxidations.
Development of new synthetic routes toward chiral "pineno-fused" N-donor ligands. Synthesis of Ru(II) complexes containing different combinations of these new ligands with other non-chiral N-N or p-P compounds. Evaluacion of the catalytic activity of these complexes in catalytic oxidation (epoxidations) and reductions (hydrogenation and transfer hydrogenation) of C=C double bonds.
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Lubatti, Frédéric. "Synthèse de nouveaux ligands organophosphorés chiraux mixtes de type P/N. Applications dans des réactions de substitution nucléophiles asymétriques sur substrats allyliques catalysées par des complexes du palladium (0)." Aix-Marseille 3, 1999. http://www.theses.fr/1999AIX30091.
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Dans la premiere partie de ce memoire, nous presentons la mise au point d'une voie de synthese d'une nouvelle famille de ligands organophosphores chiraux de type p/n. Ces ligands mixtes presentent un motif phosphore chiral derive de la (s)-(+)-2-anilinomethylpyrrolidine et analogues, et un motif azote derive de l'hydroxypyridine ou de la 8-hydroxyquinoleine. Le ligand quiphos et ses analogues ont ete prepares de maniere totalement diastereoselective au moyen de reactions d'echanges faisant intervenir des produits commerciaux tels qu'une diamine chirale, la tris(dimethylamino)phosphine et divers derives phenoliques. La deuxieme partie de ce memoire est consacree a une premiere illustration des potentialites de ces ligands en synthese asymetrique. Ces derniers ont ete introduits dans des reactions de catalyse enantioselective de substitutions nucleophiles sur substrats allyliques catalysees par des complexes du palladium (0). Les reactions d'alkylation et d'amination allyliques du 1,3-diphenylprop-2-enylacetate et 1,3-diphenylprop-2-enylethylcarbonate par divers reactifs nucleophiles conduisent aux produits de substitution avec des exces enantiomeriques atteignant 94%. Une etude cinetique qualitative a montre que ces reactions doivent etre realisees sous les conditions de curtin-hammett pour obtenir de bonnes enantioselectivites. Un mecanisme de la reaction de substitution nucleophile catalysee par le complexe pd(0)-quiphos est propose sur la base, d'une part, de la structure du complexe palladium-quiphos- 3-allyle etablie par diffraction des rayons x, et d'autre part a partir des configurations absolues des produits obtenus.
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Tolstoy, Päivi. "Synthesis and Evaluation of N,P-Chelating Ligands in Asymmetric Transition-Metal-Catalyzed Reactions : Ir-Catalyzed Asymmetric Hydrogenation and Pd-Catalyzed Asymmetric Intermolecular Heck Reaction." Doctoral thesis, Uppsala universitet, Institutionen för biokemi och organisk kemi, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-108940.
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This thesis describes synthesis of new chiral N,P ligands and their evaluation in two types of asymmetric transition-metal catalyzed reactions. The first part of the thesis describes studies in iridium-catalyzed asymmetric hydrogenation. A new class of chiral N,P ligands, imidazole-phosphines, was synthesized and evaluated in the Ir-catalyzed asymmetric hydrogenation of olefins (Paper I). The new ligands proved to be highly efficient and enantioselective in the reaction. Because the substrate scope of Ir-catalyzed asymmetric hydrogenation is still limited to certain types of test substrates, new substrate classes with importance in medicinal and materials chemistry were investigated. Vinyl fluorides were efficiently hydrogenated to fluorine-containing chiral centers by the iridium catalysts with imidazole-phosphine ligands (Paper I). To obtain CF3-bearing chiral centers, we hydrogenated CF3-substituted olefins (Paper II). Ir-catalyzed asymmetric hydrogenation was highly enantioselective for the functionalized CF3-substituted olefins and the resulting chiral products can be valuable in design of materials such as LCD screens. Ir-catalyzed asymmetric hydrogenation was also evaluated as a route to diarylmethine chiral centers (Paper III). A wide range of new chiral compounds possessing a diarylmethine chiral center was obtained. The second part of the thesis deals with asymmetric intermolecular Heck reaction utilizing N,P ligands. The N,P ligand class of thiazole-phosphines was evaluated in the Heck reaction (Paper IV) and gave high enantioselectivity. Further, the intermolecular Heck reaction was examined using computational and experimental studies (Paper V). This study led to a better understanding of the enantioselectivity in the reaction.
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Poola, Bhaskar. "Synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers and reaction chemistry of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at triosmium carbonyl clusters." Thesis, University of North Texas, 2006. https://digital.library.unt.edu/ark:/67531/metadc5608/.
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Quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been synthesized as possible specific metal host systems. The synthesis and characterization of quinoxaline-functionalized, cage-annulated oxa- and thiacrown ethers have been described. The characterization of these host systems have been fully achieved in solution by using various techniques such as IR, 1H NMR, and 13C NMR spectroscopic methods, high-resolution mass spectrometry (HRMS), elemental microanalysis, and X-ray crystallographic analysis in case of one quinoxaline-functionalized, cage-annulated oxacrown ether compound. The synthesis of the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) is described. The substitution of the MeCN ligands in the activated cluster 1,2-Os3(CO)10(MeCN)2 by the diphosphine ligand bmi proceeds rapidly at room temperature to furnish a mixture of bridging and chelating Os3(CO)10(bmi) isomers and the ortho-metalated product HOs3(CO)9[μ-(PPh2)C=C{PPh(C6H4)}C(O)N(tolyl-p)C(O)]. Thermolysis of the bridging isomer 1,2-Os3(CO)10(bmi) under mild conditions gives the chelating isomer 1,1-Os3(CO)10(bmi), whose molecular structure has been determined by X-ray crystallography. The kinetics for the ligand isomerization have been investigated by UV-vis and 1H NMR spectroscopy in toluene solution over the temperature range of 318-348 K. On the basis of kinetic data conducted in the presence of added CO and the Eyring activation parameters, a non-dissociative phosphine migration across one of the Os-Os bonds is proposed. Orthometalation of one of the phenyl groups associated with the bmi ligand is triggered by near-UV photolysis of the chelating cluster 1,1- Os3(CO)10(bmi).
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Pagliarini, Olivio. "Chimie moléculaire du niobium et du tantale dans les degrés d'oxydation IV à II : synthèse et réactivité d'alcoxydes du tantale et du bis(cyclopentadienyl)niobium (II)." Nice, 1987. http://www.theses.fr/1987NICE4131.
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ALa synthèse d'alcoolates dinucléaires diamagnétiques du tantale se fait par réduction par l'amalgame de sodium du pentachlorure de tantale en présence de l'organolithien LiOR, (R=iPr et tBu) et d'un ligand neutre(4-picoline), ou par substitution à partir d'un dérivé du tantale. Des dérivés mononucléaires paramagnétiques du tantale sont obtenus par réduction en présence d'un défaut de 4-picoline. Le réservoir d'électrons de la liaison métal-métal multiple de dérivés dinucléaires du tantale est mis à contribution pour des réactions de couplage carbone-carbone d'acétone et de polymérisation de l'alcyne activé DMAC avec formation de structure de type "fly-over". La phosphine PMe3 permet la stabilisation du niobocène en solution ; le complexe bis(cyclopentadienyl)bis(triméthylphosphine)niobium est très réactif. Les ligands PMe3 labiles favorisent la réaction du dérivé avec des substrats insaturés et des petites molécules. Certains ligands à caractère redox souple tels les porphyrines, les catéchols ou les thiolates sont susceptibles, de par leurs transferts électroniques, d'atteindre et de stabiliser des bas degrés d'oxydation du niobium et du tantale
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Margalef, Pallarès Jèssica. "Screening of modular and readily available ligand libraries for C-X (X=H, C, N and O) bond forming reactions. The use of DFT studies for catalysts optimization." Doctoral thesis, Universitat Rovira i Virgili, 2016. http://hdl.handle.net/10803/386578.
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El creixent interès per a l’obtenció de compostos enantiomèricament purs, ha conduït a un important desenvolupament de la catàlisi asimètrica. En aquest context, aquesta tesis és centra en la síntesis de vàries famílies de lligands quirals altament modulars a partir de compostos de fàcil disponibilitat. Concretament, s'ha treballat en la síntesis de lligands fosfit-tioèter, fosfit-piridina, fosfit-triazola i lligands hidroaximida i tioamida. Tots ells tenen en comú que són sòlids, estables i per tant de fàcil manipulació. Aquests lligands s'han aplicat en la hidrogenació d’olefines funcionalitzades i no funcionalitzades catalitzada per Rh i Ir, en la reducció de cetones mitjançant transferència d’hidrogen catalitzada per Rh i Ru, en reaccions de substitució alílica catalitzada per Pd i en l'addició d'organoaluminats a aldehids catalitzada per Ni. A més a més, en alguns casos s'han realitzat estudis DFT per tal d'agilitzar el procés d'optimització dels lligands. Així doncs, s'ha aconseguit l'obtenció de diferents compostos químics quirals d'alt interès sintètic (alcohols, alcans funcionalitzats i no funcionalitzats, al·lils substituits) en grans enantioselectivitats i en el millor dels casos s'han aconseguit els productes en la seva forma enantiomèricament pura (>99% ee).El creciente interés para la obtención de compuestos enantioméricamente puros para la obtención de compuestos enantioméricamente puros, ha conducido a un importante desarrollo de la catálisis asimétrica. En este contexto, esta tesis se centra en la síntesis de varias familias de ligandos quirales altamente modulares a partir de compuestos de fácil disponibilidad. Concretamente, se ha trabajado en la síntesis de ligandos fosfito-tioéter, fosfito-piridina, fosfito-triazoles y ligandos hidroaximida y tioamida. Todos ellos tienen en común que son sólidos, estables y por lo tanto de fácil manipulación. Estos ligandos se han aplicado en la hidrogenación de olefinas funcionalizadas y no funcionalizadas catalizada por Rh e Ir, en la reducción de cetonas mediante transferencia de hidrógeno catalizada por Rh y Ru, en reacciones de sustitución alílica catalizada por Pd y en el adición de organoaluminiatos a aldehídos catalizada por Ni. Además, en algunos casos se han realizado estudios DFT para agilizar el proceso de optimización de los ligandos. Así pues, se ha logrado la obtención de diferentes compuestos químicos quirales de alto interés sintético (ej. alcoholes, alcanos funcionalizados y no funcionalizados, alilos sustituidos) en grandes enantioselectividades y en el mejor de los casos se han conseguido los productos en su forma enantioméricamente pura (> 99% ee).
The growing interest in obtaining enantiomerically pure compounds in obtaining enantiomerically pure compounds has led to a significant development in the field of asymmetric catalysis. In this context, this thesis is focused on the synthesis of several families of highly modular chiral ligands from readily available compounds. Specifically, we worked on the synthesis of thioether-phosphite ligands, phosphite-pyridine, phosphite-triazole and hidroaximide and thioamide ligands. They all have in common that are solid, stable and therefore easy to handle. These ligands have been applied in the Rh- and Ir-catalyzed hydrogenation of functionalized and unfunctionalized olefins, in the Ru- and Rh-catalyzed asymmetric transfer hydrogenation of ketones, in Pd-catalyzed allylic substitution reactions and in the Ni-catalyzed addition of organoalumininum to aldehydes. Moreover, in some cases DFT studies have been performed to speed up the optimization of ligands. Hence, a variety of chiral chemical compounds of high synthetic interest (i. e. alcohols, functionalized and non-functionalized alkanes, substituted allyl) lhigh enantioselectivities were achieved and in some cases the products were obtained in their enantiomerically pure form(> 99% ee).
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Nonglaton, Guillaume. "Applications des films Langmuir-Blodgett à base de phosphonates de zirconium pour la préparation de puces à oligonucléotides : synthèse de ligands hybrides P/N chiraux. Étude de leurs propriétés de coordination." Nantes, 2005. http://www.theses.fr/2005NANT2054.
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Ce mémoire traite d'un procédé de préparation de puces à ADN utilisant un support de verre recouvert d'une couche de phosphonate de zirconium déposée par la technique de Langmuir-Blodgett. Les oligonucléotides sondes modifiés par un phosphate terminal sont déposés sur la surface de zirconium et s'y fixent en formant des liaisons à caractère fortement covalent. Les performances de ce nouveau type de puce à ADN ont été étudiées dans des conditions biologiques. Une augmentation de la fluorescence est observée lors de l'introduction d'un espaceur polyguanine entre la sonde et le phosphate terminal. Puis la synthèse de ligands P/N chiraux est décrite via la désymétrisation du squelette méso et achiral d'une diamine de symétrie C2 par l'introduction sélective d'un groupement diphénylphosphine sur un des deux centres azotés. La coordination du ligand (L) avec des précurseurs métalliques à base de Rh(I) ou de Pd(0) permet l'obtention de complexes potentiellement utilisables en catalyseThis report deals with a new process for preparing DNA microarrays using glass slides covered by a zirconium phosphonate monolayer deposited by Langmuir-Blodgett method. Oligonucleotides probes modified with a terminal phosphate were spotted onto the zirconated surface where they bound by formation of metal-oxygen covalent bonds. Performances of this new type of DNA microarrays were studied in biological conditions. An increase of the fluorescence intensity was observed when using a polyguanine spacer between the probe oligomer and the terminal phosphate. Then the synthesis of novel chiral P,N-ligands by desymmetrization of the achiral meso N,N'-dimethyl-1,2-diphenylethane-1,2-diamine backbone is described. This transformation was achieved by the selective introduction of a diphenylphosphine moiety on one of the two nitrogen centers. The coordination of this ligand (L) with Rh(I) and Pd(0) precursors led to the formation of complexes which can be of potential interest for catalysis
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Nascimento, Fábio Batista do. "Estudos cinéticos e fotoquímicos de compostos de Ru(II) com ligantes bipiridínicos e bifosfínicos de fórmula geral cis- [RuCl2(P-P)(N-N)] (P-P = bifosfinas e N-N N-heterocíclicos bidentados)." Universidade Federal de São Carlos, 2010. https://repositorio.ufscar.br/handle/ufscar/6261.
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Previous issue date: 2010-10-14Universidade Federal de Sao Carlos
In this thesis it were studied substitution reactions in ruthenium complexes of the type cis-[RuCl2(P-P)(N-N)] and cis-[RuCl2(dppb)(N-O)] (P-P = dppm, dppe, dppp and dppb; N-N = bipy, Me-bipy, MeO-bipy, Cl-bipy and fen; N-O = 2-acpy, 2-bzpy and 2- dpk). For all complexes, in a period of 24 hours, there was only the substitution of a chloride (Cl-) coordinated to the metal. The ligands used in substitution reactions and kinetic studies were: py, 4-pic and coordenant solvents (CH3CN and PhCN). Only the Cl- trans positioned to P of diphosphines was labilized giving rise to the entering ligand, confirming the greater trans effect of phosphine ligands in relation to N-N and N-O. The mechanism attributed to substitution reactions was dissociative because the reactions do not show dependence of ligand entry. DFT calculations showed the effective participation of the Cl atom trans to the P atom of the diphosphines in the formation of the HOMO orbital. This fact shows that the reactivity of Cl atoms is different and they can be replaced selectively. Good linearity was observed for the percentage of participation of d orbitals of ruthenium in the formation of HOMO for the dissociation of Cl- complex indicating that the strength of the Ru-Cl- bond is due to the direct interaction of the orbitals of Cl- and the d orbitals of ruthenium. Exploratory studies using irradiation of light at fixed wavelengths were performed to study possible influence of the effect of the exchange rate of Cl- and also on the isomerization reaction trans/cis-[RuCl2(dppb)(bipy)]. An increase in the rate of exchange reaction was observed in the kinetics of substitution. In the isomerization processes were not observed. The substitution reactions of Cl- in the complexes cis- [RuCl2(dppb)(N-N)] (N-N = bipy and phen) by nitrile ligands (e.g. PhCN and CH3CN), lead to the formation of complexes in which trans ligands L were coordinated by the nitrogen atom of the ligands N-N in the final complex. However, studies of 31P{1H} NMR and cyclic voltammetry confirmed that the reactions take place initially with the replacement of L trans to P atom followed by an isomerization process. This is attributed to the strong competition of π between nitrile and phosphine ligands, and its final position is determined by this effect.
Nesta tese de doutorado foram estudadas reações de substituição em complexos de rutênio do tipo cis-[RuCl2(P-P)(N-N)] e cis-[RuCl2(dppb)(N-O)] (P-P = dppm, dppe, dppp e dppb; N-N = bipy, Me-bipy, MeO-bipy, Cl-bipy e fen; N-O = 2-acpy, 2-bzpy e 2-dpk). Para todos os complexos, num período de 24 horas, observou-se apenas a substituição de um cloreto (Cl-) coordenado ao metal. Os ligantes usados nas reações de substituição e nos estudos cinéticos foram: py, 4-pic e solventes coordenantes (CH3CN e PhCN). Apenas o Cl- trans posicionado ao átomo de P das bifosfinas foi labilizado, dando lugar ao ligante de entrada, confirmando o maior efeito trans da fosfina em relação aos ligantes N-N e N-O. O mecanismo atribuído para as reações de substituição foi dissociativo, pois as reações não apresentam dependência do ligante de entrada. Cálculos de DFT mostraram a participação efetiva, apenas do átomo de Cl trans ao átomo de P da bifosfina na formação dos orbitais HOMO. Este fato nos mostra que a reatividade desses átomos de Cl é diferente e os mesmos podem ser substituídos de maneira seletiva. Boa linearidade foi observada em relação à porcentagem de participação dos orbitais d do rutênio na formação de HOMO em relação às constantes de dissociação de Cl- nos complexos, indicando que a força da ligação Ru-Cl- é devido à interação direta dos orbitais de Cle os orbitais d do rutênio. Estudos exploratórios, utilizando irradiação de luz em comprimentos de onda fixados, foram realizados a fim de se observar o efeito da mesma na velocidade de troca de Cl- e também na reação de isomerização trans/cis-[RuCl2(dppb)(bipy). Apenas nas cinéticas de substituição foi observado um aumento na velocidade da reação de troca e nas reações de isomerização não observamos nenhum efeito. Nas reações de substituição de Cl- nos complexos cis- [RuCl2(dppb)(N-N)] (N-N = bipy e fen), pelos ligantes nitrila (PhCN e CH3CN), observou-se a formação de complexos onde o ligante L estava coordenado trans ao átomo de nitrogênio dos ligantes N-N no complexo final. Contudo, estudos de RMN 31P{1H} e voltametria cíclica confirmaram que a reação se dá, inicialmente com a substituição de L trans ao átomo de P seguido por uma isomerização. Este efeito foi xvii atribuído à forte competição π entre os ligantes nitrila e fosfínicos, sendo sua posição final decidida por este efeito.
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Hulmes, David. "An axially chiral P,N ligand for asymmetric homogeneous catalysis." Thesis, University of Oxford, 1994. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.359505.
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Schnoor, Ann-Christin [Verfasser]. "Molybdänkomplexe mit gemischten N/P-Liganden / Ann-Christin Schnoor." Kiel : Universitätsbibliothek Kiel, 2018. http://d-nb.info/1162892544/34.
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Silva, Juliana Paula da. "Complexos de rutênio (II) contendo ligantes aminofosfínicos do tipo P-N-P e P-N-PY : síntese, caracterização, reatividade e atividade biológica." reponame:Repositório Institucional da UFPR, 2016. http://hdl.handle.net/1884/49391.
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Orientador : Prof. Dr. Marcio Peres de AraújoTese (doutorado) - Universidade Federal do Paraná, Setor de Ciências Exatas, Programa de Pós-Graduação em Química. Defesa: Curitiba, 09/03/2016
Inclui referências : f. 128-138
Resumo: No presente trabalho, quatro ligantes aminofosfínicos do tipo P-NR-P (R = CH2py, CH2Ph, Ph, p-tol) foram sintetizados e a reatividade dos mesmos foi avaliada frente a diferentes complexos precursores, tais como [RuCl2(PPh3)3] e [RuCl2(CO)(dmf)(PPh3)2]. Essas sínteses resultaram em duas series de compostos: [RuCl2(CO)(P-NR-P)(PPh3)] e trans - [RuCl2(P-NR-P)2]. Os produtos contendo o ligante carbonilo foram analisados por RMN de 31P {1H} e espectroscopia vibracional na região do infravermelho. Os complexos de formula geral trans - [RuCl2(P-N-P)2] foram caracterizados por de RMN de 31P {1H} e 1H e a exposição desse composto a luz ambiente durante três dias deu origem ao seu isomero cis. Para os complexos trans - [RuCl2(P-NCH2Ph-P)2] e cis-[RuCl2(CO)(PPh3)(P-NCH2py-P)] foram obtidos monocristais que confirmaram as estruturas propostas. Posteriormente, ligantes aminofosfínicos do tipo P-NR-py (R= H, CH3, CH2Ph) foram sintetizados. Duas novas series de complexos foram obtidos a partir da reação entre o precursor [RuCl2( 6-pcimeno)] 2 e os ligantes P-NR-P e P-NR-py. A serie 1 consiste em quatro complexos com formula geral [RuCl( 6-p-cimeno)(P-NR-P)]+ [R = CH2py (1a), CH2Ph (1b), Ph (1c), p-tol (1d)] e a serie 2 e formada por tres complexos com formula geral [RuCl( 6-p-cimeno)(PNR- py)]BF4 [R= H (2e), Me (2f), CH2Ph (2g)]. Para a serie 1 foram isolados complexos com BF4 - e com PF6 - como contra íon. Os compostos das series 1 e 2 foram caracterizados por RMN de 31P {1H} e 1H, espectroscopia vibracional na região do infravermelho, espectrometria de massas, condutividade molar, analise elementar e difração de raios-X. Para os complexos da serie 1 foram realizados experimentos de voltametria cíclica a fim de entender o comportamento eletroquímico dos compostos. Além disso, foi avaliada a reatividade desses complexos frente a moléculas pequenas tais como: CH3CN, DMSO e NaOMe, a fim de investigar as reações de substituição. Os complexos da serie 1 foram testados como catalisadores em reações de redução da acetofenona e tiveram o seu potencial citotóxico avaliado frente a duas linhagens de células cancerígenas (MDA-MB 231 e HeLa). Esses mesmos compostos também foram testados como agentes anti- Mycobacterium tuberculosis. Palavras-chave: rutênio, ligantes aminofosfínicos, cimeno, catalise, atividade biológica.
Abstract: In this study, four P-NR-P (R = CH2py, CH2Ph, Ph, p-tol) aminophosphine ligands were synthesized and their reactivity was evaluated with different ruthenium precursors complexes, such as [RuCl2(PPh3)3] and [RuCl2(CO)(dmf)(PPh3)2]. These syntheses resulted in two series of compounds: [RuCl2(CO)(P-NR-P)(PPh3)] and trans-[RuCl2(P-NRP) 2]. The products containing carbonyl ligands were analyzed by 31P {1H} NMR and vibrational spectroscopy in the infrared region. The complexes with general formula trans- [RuCl2(P-N-P)2] were characterized by 31P NMR {1H} and 1H and it was found that upon exposure to white light for 3 days gave the cis isomer. The slow evaporation of a DCM solution containing the complex trans-[RuCl2(P-NCH2Ph-P)2] and cis-[RuCl2(CO)(PPh3)(PNCH2py- P)] yielded suitable single crystals and their DRX analysis confirmed the proposed structure. Subsequently, P-NR-py (R = H, CH3, CH2Ph) type aminophosphine ligands were synthesized. Two new series of complexes were obtained from the reaction between the precursor [RuCl2( 6-p-cymene)]2 with P-NR-P and P-NR-py ligands. The series 1 consists in four complex with general formula [RuCl( 6-p-cymene)(P-NR-P)]+ [R = CH2py (1a), CH2Ph (1b), Ph (1c), p-tol (1d) ] and the series 2 is formed by three complex with general formula [RuCl( 6-p-cymene)(R-NR-py)]+ [R = H (2e), Me (2f), CH2Ph (2g)]. The compounds of both series were characterized by 31P {1H} and 1H NMR, vibrational spectroscopy in the infrared region, mass spectrometry, molar conductivity, elemental analysis and X-ray diffraction. For complexes of series 1, cyclic voltammetry experiments were carried out to understand the electrochemical behavior of these compounds. Furthermore, the reactivity of such complexes was evaluated against small molecules such as CH3CN, DMSO, and NaOMe in order to investigate ligand substitution. Complexes of series 1 were tested as catalysts for reduction of acetophenone reactions and their cytotoxic potential was evaluated against two cancer cell lines (MDA-MB 231 and HeLa cells). They also were tested as anti-tuberculosis agent. Keywords: ruthenium, aminophosphine ligands, cymene, catalysis, biological activity.
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Figge, Axel. "Darstellung und Anwendung von P,N-Liganden mit Imidazol-Rückgrat." [S.l.] : [s.n.], 2005. http://deposit.ddb.de/cgi-bin/dokserv?idn=978283384.
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Hille, Toni [Verfasser], and Rhett [Akademischer Betreuer] Kempe. "P,N,P-Ligand-stabilisierte Iridium-Komplexe und deren Anwendung in der Nachhaltigen N-Heterozyklen-Synthese / Toni Hille ; Betreuer: Rhett Kempe." Bayreuth : Universität Bayreuth, 2017. http://d-nb.info/1147467218/34.
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Gamer, Michael. "P-N-Liganden in der Komplexchemie der Seltenerdmetalle Synthese - Charakterisierung - Katalyse /." [S.l. : s.n.], 2003. http://www.diss.fu-berlin.de/2003/241/index.html.
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Rodrigues, Claudia. "Estudo sobre o mecanismo de reações de hidrogenação em complexos do tipo [RuCl2(P)2(N)2][(P)2= mono ou bifosfina; N= piridina ou derivados]." Universidade Federal de São Carlos, 2010. https://repositorio.ufscar.br/handle/ufscar/6472.
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Previous issue date: 2010-03-26Universidade Federal de Sao Carlos
In this study, it was performed synthesis and characterization of the complexes of general formula cis-[RuCl2(PPh3)2(N)2], cis-[RuCl2(PPh3)2(N-N)], trans- [RuCl2(dppb)(N)2], cis-[RuCl2(dppb)(N-N)] and cis-[RuCl2(P-P)(N-N)] [PPh3 = triphenylphosphine, dppb = 1,4-bis(diphenylphosphino)butane, (P-P) = bis(diphenylphosphino)methane, 1,2-bis(diphenylphosphino)ethane and 1,3- bis(diphenylphosphino)propane, N = pyridine (py), 4-picoline (4-pic), 4-tertbutilpyridine (4t-Bupy ), 4-vinylpyridine (4-vpy) and 4-phenylpyridine (4-Phpy), N-N = 2,2'-bipyridine (bipy), 1,10-phenanthroline (phen), 4,4'-dimethyl-2,2'-bipyridine (4- Mebipy), di-2-piridilcetona (dpk) and 4,4'-dimethoxy-2,2'-bipyridine (MeO-bipy)]. The characterizations were performed using elemental analysis, conductivity, Infrared spectrometry (IR), NMR 31P {1H}, cyclic voltammetry and differential pulse voltammetry as well as X-ray diffraction, when suitable crystals were obtained. Kinetic studies of substitution of one chloride ligand from the coordination sphere of the complex by a monodentate L ligand (pyridine (py) or 4-picoline (4-pic)) were performed for the complex series of cis-[RuCl2(P-P)(N-N)] in terms of pseudo-first order conditions. The catalytic studies of some of the complex obtained in this work in hydrogenation reactions of cyclohexene were carried out. For the catalytic reactions were used a stainless steel reactor purging with H2 pressure, temperature and agitation were controlled and the analysis of results were performed in a gas chromatograph with detector flame ionization detector (GC-FID) with a capillary column DB5. The catalytic reactions performed with the complex series of [RuCl2(PPh3)2(N)2] showed a high conversion of reactant (cyclohexene - CXE) to product (cyclohexane - CXA) and a high value of TOF (turnover frequency) above 1000 h-1, during 24 hours of reaction. For complex series of [RuCl2(dppb)(N)2] the values of conversion (%) and TOF (h-1) were not as high, but still significant. For the other tested complexes, the values were low and the conversions were not significant.
Neste trabalho, realizaram-se as sínteses e caracterizações dos complexos de fórmula geral cis-[RuCl2(PPh3)2(N)2], cis- [RuCl2(PPh3)2(N-N)], trans-[RuCl2(dppb)(N)2], cis-[RuCl2(dppb)(N-N)], cis-[RuCl2(PP)( N-N)] [PPh3 = trifenilfosfina, dppb = 1,4-bis(difenilfosfina)butano, (P-P) = bis(difenilfosfina)metano, 1,2-bis(difenilfosfina)etano e 1,3-bis(difenilfosfina)propano; N = piridina (py), 4-picolina (4-pic), 4-terc-butilpiridina (4t-Bupy), 4-vinilpiridina (4-Vpy) e 4-fenilpiridina (4-Phpy); N-N = 2,2 -bipiridina (bipy), 1,10-fenantrolina (fen), 4,4 - dimetil-2,2 -bipiridina (4-Mebipy), di-2-piridilcetona (dpk) e 4,4 -dimetoxi-2,2 -bipiridina (MeO-bipy)]. As caracterizações foram realizadas por meio de análise elementar, condutividade, espectroscopia de absorção na região do infravermelho (IV), RMN de 31P{1H}, voltametria cíclica e voltametria de pulso diferencial e difração de raios X, quando se obteve cristais. Os estudos cinéticos de substituição de um ligante cloreto da esfera de coordenação do complexo por um ligante L monodentado (piridina (py) ou 4-picolina (4-pic)) foram realizados para os complexos da série cis-[RuCl2(P-P)(NN)] em condições de pseudo primeira ordem. Os estudos catalíticos de alguns dos complexos obtidos durante este trabalho em reações de hidrogenação do cicloexeno foram realizados. Para as reações catalíticas foi utilizado um reator de aço inox com pressão de H2, temperatura e agitação controladas e as análises dos resultados foram realizadas em um cromatógrafo a gás com detector de ionização por chama (GC-FID) com coluna capilar DB5. As reações catalíticas realizadas com os complexos da série [RuCl2(PPh3)2(N)2] apresentaram uma alta conversão de reagente (cicloexeno - CXE) em produto (cicloexano - CXA) e um alto valor de TOF (turnover frequency) acima de 1000 h-1, em 24 horas de reação. Para os complexos da série [RuCl2(dppb)(N)2] os valores de conversão (%) e TOF (h-1) não foram tão altos, mas ainda são significativos. Para os demais complexos testados, os valores encontrados foram baixos e as conversões não foram significativas.