Literatura académica sobre el tema "Seconde sphère de coordination"
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Artículos de revistas sobre el tema "Seconde sphère de coordination"
Raymo, Françisco M. y J. Fraser Stoddart. "Second-Sphere Coordination". Chemische Berichte 129, n.º 9 (septiembre de 1996): 981–90. http://dx.doi.org/10.1002/cber.19961290902.
Texto completoLiu, Zhichang, Severin T. Schneebeli y J. Fraser Stoddart. "Second-Sphere Coordination Revisited". CHIMIA International Journal for Chemistry 68, n.º 5 (28 de mayo de 2014): 315–20. http://dx.doi.org/10.2533/chimia.2014.315.
Texto completoAndo, Isao, Koji Nishihara, Kikujiro Ujimoto y Hirondo Kurihara. "Effect of second-sphere coordination." Inorganica Chimica Acta 346 (marzo de 2003): 19–24. http://dx.doi.org/10.1016/s0020-1693(02)01426-3.
Texto completoRAYMO, F. M. y J. F. STODDART. "ChemInform Abstract: Second-Sphere Coordination". ChemInform 27, n.º 48 (4 de agosto de 2010): no. http://dx.doi.org/10.1002/chin.199648270.
Texto completoLOEB, S. J. "ChemInform Abstract: Second-Sphere Coordination". ChemInform 28, n.º 2 (4 de agosto de 2010): no. http://dx.doi.org/10.1002/chin.199702222.
Texto completoAllély, Annie. "Les enfants malformés et handicapés à Rome sous le Principat". Revue des Études Anciennes 106, n.º 1 (2004): 73–101. http://dx.doi.org/10.3406/rea.2004.6413.
Texto completoBlight, Barry A., Kevin A. Van Noortwyk, James A. Wisner y Michael C. Jennings. "[2]Pseudorotaxanes through Second-Sphere Coordination". Angewandte Chemie International Edition 44, n.º 10 (25 de febrero de 2005): 1499–504. http://dx.doi.org/10.1002/anie.200462380.
Texto completoBlight, Barry A., Kevin A. Van Noortwyk, James A. Wisner y Michael C. Jennings. "[2]Pseudorotaxanes through Second-Sphere Coordination". Angewandte Chemie 117, n.º 10 (25 de febrero de 2005): 1523–28. http://dx.doi.org/10.1002/ange.200462380.
Texto completoLiu, Zhichang, Severin T. Schneebeli y J. Fraser Stoddart. "ChemInform Abstract: Second-Sphere Coordination Revisited". ChemInform 45, n.º 42 (2 de octubre de 2014): no. http://dx.doi.org/10.1002/chin.201442260.
Texto completoCucos, Andrei, Andrei Ursu, Augustin M. Madalan, Carine Duhayon, Jean-Pascal Sutter y Marius Andruh. "Co-crystallization of coordination compounds through second-coordination sphere interactions". CrystEngComm 13, n.º 11 (2011): 3756. http://dx.doi.org/10.1039/c1ce05112a.
Texto completoTesis sobre el tema "Seconde sphère de coordination"
Meunier, Antoine. "Les foldamères comme mimes de la seconde sphère de coordination des hydrogénases [Fe-Fe]". Thesis, Bordeaux, 2017. http://www.theses.fr/2017BORD0826/document.
Texto completoThe ability to replicate enzymatic activity with a synthetic molecule is a highly sought after goal in modern chemistry. However, it remains a big challenge even in case of activation of small molecules. In the case of hydrogen, some bacteria can use it as energy carrier by means of enzymes called hydrogenases that can reversely make or break the bond of hydrogen molecules and are made of earth abundant metals. As hydrogen could be used for the same purpose of energy storage in our society, hydrogenases caught interest of scientific community. To date, most biomimetic hydrogenase models mainly focus on first coordination sphere modifications to fine-tune structure and physical properties. However, point mutation studies indicate that several of the amino acid residues surrounding the enzyme active site are required for structural stability or high turnover frequencies. It shows how mimicking second coordination sphere could improve the capabilities of synthetic catalysts. Our approach used aromatic oligoamide foldamers as helical scaffolds around an inspired 2Fe2S4cluster. Convergent synthesis of the final molecule and structural studies in the solid state (x-ray) and in solution (NMR, IR) as well as the dynamic behaviour are reported. Modifications of the first coordination sphere of the model complex in presence of the foldamer are also described, showing interactions between them
De, Leener Gaël. "Nouveaux complexes biomimétiques dérivés de calix[6]azacryptands :étude des effets de seconde sphère et greffage sur surface". Doctoral thesis, Universite Libre de Bruxelles, 2016. http://hdl.handle.net/2013/ULB-DIPOT:oai:dipot.ulb.ac.be:2013/228642.
Texto completoPlus de 30% des enzymes présentent un ion métallique dans leur site actif qui est la clé pour les réactions de catalyse. Une sous-famille d’enzymes comporte un site actif où un seul ion métallique (Zn2+ ou Cun+) est coordiné à un cœur polyhistidine. L’élaboration de composés modèles est important pour la compréhension des mécanismes fondamentaux impliqués dans le cycle biocatalytique de ces enzymes mononucléaires. Dans ce contexte, nous avons développé des ligands basés sur des calix[6]arènes présentant un chapeau polyazoté lié de manière covalente au macrocycle. Ces ligands offrent un site de coordination pour le métal et une cavité hydrophobe bien définie. Cet assemblage permet et contrôle la liaison d’un ligand exogène dans la cavité. Afin de moduler les propriétés des complexes métalliques calixaréniques basés sur une unité coordinante tren (tris(2-aminoéthyl)amine), nous avons synthétisé avec succès et étudié plusieurs nouveaux récepteurs calix[6]aréniques.La synthèse de récepteurs bisétagés, le calix[6]amido-tren et le calix[6]amido-tacn, a permis de modifier la seconde sphère de coordination par incorporation de groupements amide entre la cavité et le site de coordination. Cette stratégie s’est avérée efficace. En effet, la coordination d’anions au centre métallique a été mise en évidence et en particulier celle simultanée de deux Cl pour le Cu-calix[6]amido-tren. Cette coordination d’un ou plusieurs invités anioniques était impossible dans le cas du calix[6]tren parent qui présente une seconde sphère de coordination électroniquement dense et un chapeau trop petit pour y accueillir plusieurs invités. La présence de groupements carbonyle entre la chapeau tren et le calixarène modifie également le comportement des complexes :leur coordination au centre métallique entre en compétition avec celle d’invités exogènes. L’oxydation d’amines encombrées sous O2 en hydroxylamines et oximes a été réalisée par la réduction du complexe cuivrique du calix[6]amido-tren par électrochimie. Ce type d’amines n’est pas oxydable par l’adduit superoxo du complexe parent, dû à la taille de la cavité qui empêche la coordination d’invités encombrés. De plus, la formation d’un adduit superoxo a été mise en évidence qualitativement au départ du complexe cuivreux isolé de ce même composé. Ces résultats permettent d’envisager des études de réactivité mimant le site actif des enzymes PHM et DβM par exemple. Enfin, une comparaison des propriétés hôte-invité et de la réactivité des complexes du calix[6]amido-tren avec celles des complexes du calix[6]amido-tacn a été réalisée afin d’évaluer l’impact de la nature du chapeau polyazoté sur les propriétés hôte-invité et la réactivité de ces complexes.Une méthodologie de déméthylation assistée de manière supramoléculaire a été développée pour différents calix[6]azacryptands chapeautés. Celle-ci a ensuite été appliquée avec succès à la déméthylation du calix[6]tren pour obtenir le calix[6]trentrisPhOH. Ce récepteur a montré un comportement très différent de celui du récepteur parent. En effet, la complexation d’anions et d’ammoniums biologiquement pertinents a été possible par ce récepteur protonné. L’interaction entre le centre métallique et les phénates en présence de base a conduit à la réalisation d’un switch moléculaire multi-étapes entre différents états de protonation du récepteur et du complexe zincique. Son complexe cuivrique a montré la présence d’un radical phénoxyle après oxydation du phénate. Cette espèce CuII-radical phénoxyle mime la forme oxydée du site actif de la galactose oxydase, catalysant l’oxydation d’alcools en aldéhydes. Ces résultats ouvrent donc la voie à de nouvelles perspectives pour les études de réactivité de ce composé.Un analogue du calix[6]tren, porteur d’un bras avec une fonction réactive sur le chapeau, a été synthétisé et complexé au cuivre avant d’être immobilisé sur surface via la formation de monocouches. Les électrodes ainsi modifiées ont été étudiées en milieu organique et aqueux. En milieu organique, les propriétés hôte-invité du calix[6]tren sont conservées après immobilisation. En milieu aqueux, un système redox réversible a été observé. Celui-ci a permis la détection sélective d’alkylamines linéaires par le système à pH basique. A notre connaissance, il s’agit du premier système supramoléculaire à cuivre, immobilisé sur surface, qui permet cette détection en milieu aqueux.
Doctorat en Sciences
info:eu-repo/semantics/nonPublished
Smith, Adrien. "Activation and reduction of CO2 by metalloporphyrin-based molecular catalysts". Electronic Thesis or Diss., université Paris-Saclay, 2024. http://www.theses.fr/2024UPASF039.
Texto completoTransforming CO₂ into valuable reduced forms of carbon is an interesting approach towards the recycling of this greenhouse gas, by introducing non-fossil fuel based C1 building blocks back into the carbon cycle. Tetraphenyl iron porphyrins and derivatives have been shown to be efficient and selective molecular catalysts for CO₂ reduction to CO. The introduction of various functions in the second coordination sphere of porphyrins showed great improvements of both the overpotential and the catalytic rates.Inspired by the distal pocket of enzymatic active centers, an iron porphyrin with a carboxylate strap is investigated. Electrochemical, kinetic and computational chemistry studies show that this catalyst operates at a low overpotential, while maintaining high catalytic rates. It is proposed that the carboxylate function, initially acting as an axial ligand of the metal, plays an important role in the insertion and transformation of CO₂, in synergy with a water molecule trapped in the superstructure.Furthermore, two iron porphyrins were synthetized bearing an imidazolium group at various positions with respect to the metal center. The original goal of this study was to establish a correlation between the distance of the cationic group from the metal center and the catalytic performances of the catalyst, which can guide the design of new catalysts for CO₂ reduction.The electrochemical study of these catalysts revealed that these imidazolium functions can be electroactive. Electron paramagnetic resonance was used to describe their various reduced forms. These studies revealed and describe the potential electroactive behavior of the imidazolium groups on these novel iron porphyrins catalysts
Yaccato, Karin J. "The second sphere coordination of peroxovanadium guests with polyurea, polyguanidinium and polyammonium hosts". Thesis, National Library of Canada = Bibliothèque nationale du Canada, 1998. http://www.collectionscanada.ca/obj/s4/f2/dsk1/tape10/PQDD_0001/MQ44317.pdf.
Texto completoKaczorowski, Florence. "Les américaines et la politisation de la sphère privée dans l'après seconde guerre mondiale". Thesis, Lille 3, 2016. http://www.theses.fr/2016LIL30048/document.
Texto completoThis thesis examines various factors that have led to the reconfiguration of the private / domestic sphere, considered as the non-political domain of the family and the intimate, as a crucial subject for political debate and as a legitimate place of political action in the aftermath At the heart of the process were three major phenomena: the militarization of private civil space, the resurgence of the ideal of the "Christian home" in a moralist and familialist climate, and the valorization of the home Consumerism, the "center of freedom", where the defense of the capitalist system was played out in the ideological conflict between the United States and the USSR During this period, the private-public articulation was renegotiated, thanks to the phenomenon of politicization of the private sector and the additional legitimacy granted to the stakes associated with this domain and, by extension, to the women who are supposed to guarantee the integrity . Three case studies, based on rich archival sources that have so far been largely untapped, make it possible to take full account of this renegotiation and to account for the adoption of new forms of policy-making at home ('kitchen-table activism ') By a large number of white women of the middle-upper classes. This mode of activism, reconciling domestic life, feminine sociability and militant commitment, was put to the service of progressive and conservative women's organizations as well as women's divisions of political parties. To what extent did its expansion reflect the politicization of its followers and the rise of their political participation during a latent period of the feminist movement ? Have their involvement in the margins of the institutional sphere been accompanied by an increase in their representation in politics ? Or did the period, on the contrary, see their advance in this delayed field because of this mobilization based on a traditional view of women and gender relations ?
Graves, Amanda. "Second coordination sphere of heme in Mycobacterium tuberculosis MhuD, and the mechanism of heme degradation". ScholarWorks @ UVM, 2016. http://scholarworks.uvm.edu/graddis/645.
Texto completoBosch, Simone [Verfasser] y Peter [Akademischer Betreuer] Comba. "The Impact of the Second Coordination Sphere in Phosphatase Model Complexes / Simone Bosch ; Betreuer: Peter Comba". Heidelberg : Universitätsbibliothek Heidelberg, 2015. http://d-nb.info/1180396251/34.
Texto completoWillot, Jérémy. "Elaboration de ligands hétéropolydentes à motifs NHC-phosphine en sphère de coordination du manganèse et évaluation de leurs propriétés de coordination". Thesis, Toulouse 3, 2017. http://www.theses.fr/2017TOU30283/document.
Texto completoThis work is based on an original method for the elaboration of phosphine- N-heterocyclic carbene (NHC) polydentate ligands based on the unique reactivity of methylenephosphonium manganese (I) complexes CpMn(CO)2(eta2-R2P+=C(H)Ph) with imidazole derivatives judiciously chosen. The first chapter focuses on the polydentate ligands associating a phosphine with an N-heterocyclic carbene, their variety, their methods of synthesis and their applications in the field of homogeneous catalysis. The second chapter is dedicated to the synthesis of a variety of methylenephosphonium complexes CpMn(CO)2(eta2-R2P+=C(H)Ph from cymantrene CpMn(CO)3 and secondary phosphines HPR2 carrying different groups on the phosphorus atom whose 2,5-diphenylphospholane derivative available in optically active version. Spectroscopic, structural and theoretical studies have made it possible to understand the electronic structure of methylenephosphonium complexes and to rationalize their reactivity towards nucleophiles, which turns out to be in contrast to that of free methylenephosphonium salts. The third chapter describes the preparation of a library of phosphine-C(H)Ph-imidazolium pre-ligands by nucleophilic attack of a substituted imidazole (ImR') on methylenephosphonium complexes followed by a step of demetallation of intermediate phosphine complexes CpMn(CO)2(kappa1-R2P-C(H)Ph-Im+R') by irradiation in the visible and in solution in dichloromethane. Depending on the nature of the substituent carried by the imidazole nitrogen, this approach has made it possible to directly and efficiently obtain bidentate pre-ligands (R' = alkyl or aryl), NHC core pincers carrying various arms (pyridine, thioether, NHC or phosphonium ylide) or even tetradentate architectures of bis-NHC-bis-phosphine type. The fourth chapter is devoted to preliminary studies of coordination chemistry of these new ligands with transition metals of first (Mn, Ni, Cu) and second (Rh, Pd) periodic table line. In particular, it is shown that the phosphine-NHC-pyridine trident ligand can be coordinated to the metal either in a conventional pincer mode for the RhI, RhIII and NiII complexes, or in a non-conventional bridging coordination mode between two metal atoms connected by a metallophilic interaction (CuI) or a covalent bond (Mn0). The fifth chapter focuses on the synthesis of a new family of metallasubstituted phosphorus ylide-NHC complexes obtained by selective deprotonation of the benzylidene bond in complexes incorporating R2P-C(H)Ph-NHC bidentate ligands. This type of complex, isolated in series PdII and MnI, can easily activate the C-H bond of acetonitrile or the H-H bond of dihydrogen, respectively, illustrating a new mode of metal-ligand cooperation. This last process was exploited in series MnI in catalysis of hydrogenation of ketones
De, Leener Gaël. "Nouveaux complexes biomimétiques dérivés de calix[6]azacryptands : étude des effets de seconde sphère et greffage sur surface". Thesis, Sorbonne Paris Cité, 2016. http://www.theses.fr/2016USPCB024/document.
Texto completoMore than 30% of all enzymes present a metal ion in their active site. Interesting sub-families present a mononuclear active site where a single metal ion (Zn2+ or Cun+) is coordinated to a polyhistidine core. The elaboration of model compounds is important for understanding the fundamental mechanisms involved in their bio-catalytic cycles. In this context, we have developed calix[6]arene based ligands presenting an aza cap covalently linked to the calixarene moiety. These supramolecular assemblies present several advantages: they offer a coordination site for a metal ion through the nitrogen donor atoms of the cap, the small rim of the calixarene moiety defines the second coordination sphere, and the hydrophobic cavity presents an access channel for exogenous ligands. In these systems the coordinating nitrogen atoms are separated from the oxygen rich small rim by two carbon atoms, which allows the controlled coordination of one single guest inside the cavity. Wanting to modulate the properties of the calix[6]arene tren-based (tris(2-aminoethyl)amine) ligand, we successfully synthetized several new receptors and studied their reactivity. The synthesis of “two-story” receptors, the calix[6]amido-tren and calix[6]amido-tacn, allowed the modification of the first and second coordination sphere of a coordinated metal ion by introducing an additional spacer between the tripodal aza-cap and the calixarene macrocycle. The complexes of CuI, CuII and ZnII of these new ligands were synthesized and their reactivity was studied. The presence of three potentially coordinating carbonyl groups changed the host-guest reactivity of these metal complexes as they are in competition with exogenous ligands. A comparative study of the host-guest properties and of the reactivity of the metal complexes of both ligands, calix[6]amido-tren and calix[6]amido-tacn was realized. The cavity of these “two-story” ligands is larger than the one of the parent calix[6]tren and more flexible, allowing not only the coordination of an anion, but the simultaneous coordination of two Cl¯ ligands. The oxidation of sterically hindered amines into hydroxylamines and oximes in the presence of O2 was electrochemically realized by the reduction of the cupric center forming a CuII-superoxo adduct as the reactive species. Amine oxidation has been shown for the parent complex, however, the scope of this reaction was limited due to the smaller cavity. The formation of a CuII-superoxo adduct of the calix[6]amido-tren complex was qualitatively evidenced at low temperature upon addition of O2 to the isolated cuprous complex. This type of adduct has attracted much attention in recent years since it is considered to be a reactive intermediate in the catalytic cycle of copper monooxygenases, such as PHM and DβM. A supramolecular assisted demethylation methodology was developed for different capped calix[6]azacryptands. This methodology was then successfully applied to the demethylation of calix[6]tren in order to obtain calix[6]trentrisPhOH. This receptor showed a very different behavior in comparison to the parent one. Indeed, the complexation of anions and biologically relevant ammonium ions was evidenced by the monoprotonated receptor. The metal complexes of CuII and ZnII were synthesized. The interaction between the metal center and the phenate groups in presence of base has been evidenced and has conducted to a multi-step molecular switch. The cupric complex showed the presence of a phenoxyl radical resembling the oxidized form of galactose oxidase, catalyzing the oxidation of alcohols into aldehydes. These results open the way to new perspectives in reactivity studies. An analog of calix[6]tren, bearing a functionalized reactive arm on the tren cap, was synthesized and the corresponding CuII complex was immobilized on a gold surface through a monolayer formation. (...)
Bonin, Lucie. "Etude de la spéciation des actinides vis-à-vis de ligands d'intérêt pour la décorporation". Paris 11, 2008. http://www.theses.fr/2008PA112029.
Texto completoData about the behaviour of actinides in biological media are required in order to investigate their decorporation. Those data are obtained through in vivo experiments and the study of chemical speciation of actinides within the presence of biological constituents. A part of this work consists in the development of a method leading to the determination of the speciation of actinides at the oxidation state +IV within the presence of a complexing species, as well as its structure. The method was applied to two types of ligands : 1) a constituent of blood plasma : the citrate anion. The various complexes formed were investigated and their formation constants were quantified. The coordination mode of the ligand was then clarified through a structural study of the complexes, underlining the role of only one carboxylic site and of the alcohol function. 2) chelating agents used for decorporation. The formation constants of complexes of An(IV) with NTA and DTPA were determined. The coordination number of the metallic cation in those complexes as well as the role of the nitrogen atom were proved. Lastly, the behaviour of Pu(IV) within the presence of LIHOPO was investigated. This chelating agent, more efficient than DTPA in the case of in vivo decorporation of Np, forms very stable complexes with the metallic cation. One of those complexes can be assumed to present a stoichiometry 2 :3
Capítulos de libros sobre el tema "Seconde sphère de coordination"
Jones, Leigh F. "Beyond the Metallacrown: Controlling First- and Second-Order Coordination Spheres Towards Discrete and Extended Architectures". En Advances in Metallacrown Chemistry, 221–75. Cham: Springer International Publishing, 2022. http://dx.doi.org/10.1007/978-3-031-08576-5_6.
Texto completoBeauchamp, Derek A. y Stephen J. Loeb. "Second‐Sphere Coordination". En Encyclopedia of Supramolecular Chemistry, 1209–14. CRC Press, 2004. http://dx.doi.org/10.1081/e-esmc-120012712.
Texto completoMingos, D. M. P. "Redox reactions". En Essentials of Inorganic Chemistry 2. Oxford University Press, 1998. http://dx.doi.org/10.1093/hesc/9780198559184.003.0010.
Texto completoMalcolm Charles III, R. y Timothy P. Brewster. "Chemical Transformations in Heterobimetallic Complexes Facilitated by the Second Coordination Sphere". En Topics in Organometallic Chemistry. Berlin, Heidelberg: Springer Berlin Heidelberg, 2023. http://dx.doi.org/10.1007/3418_2022_79.
Texto completoKattel, Rainer, Wolfgang Drechsler y Erkki Karo. "Agile Stability in the Post-Second World War Era". En How to Make an Entrepreneurial State, 95–122. Yale University Press, 2022. http://dx.doi.org/10.12987/yale/9780300227277.003.0004.
Texto completoVicens, Laia y Miquel Costas. "Activation of hydrogen peroxide with biologically inspired non-heme iron and manganese catalysts: From simple molecular complexes to modification of the second coordination sphere". En Advances in Inorganic Chemistry. Elsevier, 2024. http://dx.doi.org/10.1016/bs.adioch.2024.06.001.
Texto completoVialla, François, Cathie-Sophie Pinat, Alice Turinetti, Bruno Siau y Lionel Marzials. "Jurisprudences du secteur social et médico-social". En Jurisprudences du secteur social et médico-social, 105–50. Dunod, 2012. http://dx.doi.org/10.3917/dunod.vial.2012.01.0105.
Texto completoActas de conferencias sobre el tema "Seconde sphère de coordination"
Nakano, M., K. Kawamura, K. Hara y K. Amemiya. "Adsorption Site of Cs+ in Bentonite: Determination by EXAFS". En ASME 2003 9th International Conference on Radioactive Waste Management and Environmental Remediation. ASMEDC, 2003. http://dx.doi.org/10.1115/icem2003-5000.
Texto completoVukašinović Radojičić, Zorica y Dejan Vučetić. "THE EUROPEAN PRINCIPLES OF PUBLIC ADMINISTRATION SERVICES DELIVERY FROM THE PERSPECTIVE OF DIGITALIZATION AND SIMPLIFICATION : NORMATIVE FRAMEWORK AND PRACTISE IN THE REPUBLIC OF SERBIA". En International Scientific Conference “Digitalization and Green Transformation of the EU“. Faculty of Law, Josip Juraj Strossmayer University of Osijek, 2023. http://dx.doi.org/10.25234/eclic/27449.
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