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1
Robertson, A. H. Jean. "Properties of CH bonds in alkyl transition metal compounds." Thesis, University of Aberdeen, 1990. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.241468.
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This Thesis describes the results of a detailed vibrational study of a representative series of methyl and ethyl derivatives of transition metals. The primary objective of the work was to show that vibrational frequency data can be used to provide information on CH bond lengths, HCH angles and alkyl group geometries with an accuracy and reliability which is not readily attainable by other methods, and that the vibrational technique is generally applicable to a wide variety of organometallic compounds. The work involved the preparation of protonated, partially deuterated and fully deuterated examples of the molecules studied and made particular use of correlations between 'isolated' CH stretching frequencies, v15CH, measured in partially deuterated systems, and CH bond length and HCH angles. In the case of MeM(CO)2Cp (M = Fe,Ru), it is shown that, unlike related molecules of this type, the results show no evidence for a high barrier to internal rotation of the methyl group. The titanium compound MeTiCl2Cp, is shown to be non-agnostic, with the only unusual feature being an unusually low δ5CH3 frequency. In the ethyl series preliminary studies necessitated a careful re-examination of the accepted assignments for ethyl halides, leading to changes in some cases. Following this, detailed assignments are made, wherever possible, for the ethyl metal compounds, with particular emphasis on the CH stretching region. In all of the ethyl metal compounds, the α and β-CH bonds are considerably longer, and weaker, than those in the ethyl halides, and the terminal methyl group invariably contains two dissimilar types of CH bond, differing in the CH stretching frequency by as much as 58cm-1. The longer CH bonds in these ethyl compounds are trans to the metal atoms and are amongst the weakest to have been identified in alkyl metal systems.
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McIntosh, Alan Paton. "Reaction of phosphorus containing compounds with transition metal multiple bonds." Thesis, University of Edinburgh, 1988. http://hdl.handle.net/1842/30483.
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Yu, Yaqin Albrecht-Schmitt Thomas E. "Studies on the structures and properties of bimetallic uranium transition metal and hybrid organic-inorganic compounds." Auburn, Ala, 2009. http://hdl.handle.net/10415/1748.
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Graham, Andrew J. "Studies of the reactions of perfluoroarylborane Lewis acids with transition metal compounds." Thesis, University of Oxford, 1998. https://ora.ox.ac.uk/objects/uuid:1253189a-b593-496d-8fde-e9a994dc9fd1.
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This thesis describes the preparation of strongly electrophilic boranes and their reactivity with transition metal compounds. Chapter One presents an overview of the reactivity of boron-containing Lewis acids as found in the literature focusing primarily on reactions of electrophiles containing a boron-perfluoroaryl bond that are of synthetic rather than catalytic interest. Chapter Two presents studies into the reactivity of boranes of the general formula RB(C6F5)2 [R = (C6F5), Ph, H or Cl] with some metallocene hydrides. The previously synthesised adduct [(η5-C5H5)2Mo(H)(η1-HB(C6F5)3)] has been further investigated and the analogous adduct of HB(C6F5)2 is also reported. The zwitterionic compounds [(η5-C5H4B(C6F5)2R)(η5-C5H5)WH3] {R = (C6F5), Ph, H or Cl*} and [(η5-C5H4B(C6F5)3)(η5-C5H5)ReH2] are described and have been fully characterised (* indicates that an X-ray crystal structure was obtained). Investigations into the reactivity of these compounds towards competing Lewis bases have been undertaken and reveal that the rhenium zwitterion is considerably more stable than the tungsten analogues. Chapter Three presents reactions between B(C6F5)3 and transition metal nitrido complexes. B(C6F5)3 reacts directly with a number of nitrido compounds; [{(C66F5)3BN}Re(PR3)(S2CNR'2)2] (R3 = MePh2 and R' = Et*; R3 = Me2Ph and R' = Me*), [{(C6F5)3BN}ReCl(PMePh2)2(S2CNMe2)], [{(C6F5)3BN}Mo(S2CNR2)3] (R = Me or Et) and [{(C66F5)3BN}Os(1,2-S2C6H4)2][nBu4N] have all been prepared (* indicates that an X-ray crystal structure has been obtained). The reactivity of these adducts towards competing Lewis bases has been probed revealing a range of stabilities over the three metals considered. The adduct of an osmium nitrido compound has also been reacted with competing Lewis acids and the compound [{(C6F5)3BN}Os(1,2- (S)(SMe)C6H4)(1,2-S2C6H4)] has been made and characterised by NMR spectroscopy. Chapter Four describes the synthesis of Lewis acids containing a boronperfluoroaryl bond. Firstly, modified literature preparations of RB(C6F5)2 [R = (C6F5), Cl or H] are reviewed. Attempts to prepare the new Lewis acid BAr'3 [Ar' = (3,5- C6H3(CF3)2)] are described, including the synthesis and characterisation of the new tin reagent nBu3SnAr'. Additionally, the new electrophile B(C6H5)(C6F5)2 has been prepared using either nBu3Sn(C6F5) or [LiC6F5] as the source of (C6F5). Chapter Five contains experimental details for the thesis, characterising data for new compounds are presented in Chapter Six and details of the X-ray crystal structures may be found in the Appendices.
5
Grill, Joseph Michael. "The design of new ligands and transition metal compounds for the oxidation of organic compounds." [College Station, Tex. : Texas A&M University, 2006. http://hdl.handle.net/1969.1/ETD-TAMU-1746.
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McMorn, Paul. "Oxidation of selected organic compounds using transition metal containing silicates and aluminophosphates." Thesis, University of Liverpool, 1997. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.266048.
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Thu, Hung-yat. "Catalytic C-H bond functionalization reactions catalyzed by rhodium(III) porphyrin, palladium(II) and platinum(II) acetate complexes." View the Table of Contents & Abstract, 2006. http://sunzi.lib.hku.hk/hkuto/record/B38027872.
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Park, Jaena [Verfasser], and Rüdiger [Akademischer Betreuer] Klingeler. "High-field Electron Spin Resonance study on Correlated Transition Metal Compounds and Metal-Organic Compounds / Jaena Park ; Betreuer: Rüdiger Klingeler." Heidelberg : Universitätsbibliothek Heidelberg, 2015. http://d-nb.info/1180608984/34.
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Carson, Cantwell G. "Noble and transition metal aromatic frameworks synthesis, properties, and stability /." Diss., Atlanta, Ga. : Georgia Institute of Technology, 2009. http://hdl.handle.net/1853/29657.
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Thesis (Ph. D.)--Materials Science and Engineering, Georgia Institute of Technology, 2009.Committee Chair: Rina Tannenbaum; Committee Co-Chair: Rosario A. Gerhardt; Committee Member: E. Kent Barefield; Committee Member: Karl I. Jacob; Committee Member: Preet Singh; Committee Member: R. Bruce King. Part of the SMARTech Electronic Thesis and Dissertation Collection.
10
Gegham, Galstyan [Verfasser]. "Computation of Protonation Patterns for Organic Compounds and Transition Metal Complexes / Galstyan Gegham." Berlin : Freie Universität Berlin, 2014. http://d-nb.info/1060368153/34.
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William, David N. "Synthesis, reactivity and bonding of compounds containing transition metal-nitrogen multiple bonds and related studies." Thesis, Durham University, 1990. http://etheses.dur.ac.uk/6253/.
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This thesis describes studies directed towards the preparation of new transition metal species containing multiple bonds to nitrogen, with a view to learning more about the structure and reactivity of metal bound nitrogen: Chapter 1 highlights areas of transition metal nitrido and imido chemistry of relevance to the general theme of the thesis. Chapter 2 describes the use of silyl amines and amides for convenient solution syntheses of half-sandwich imido complexes of niobium and tantalum of the type CpM(NR)Cl(_2) (R = Me, Bu, 2-6-(^i)Pr(_2)C(_6)H(_3)). In addition, the preparation and characterisation of alkyl, phenoxide and alkoxide derivatives are presented. The bis-neopentyl derivative, CpNb(N(^t)Bu)(CH(_2)CMe(_3))(_2), is found to possess two a-agostic C- H interactions. Finally, attempts to prepare a bis imido species of the type [CpNb(NR)(_2)] are discussed. Chapter 3 employs Fenske-Hall quantum chemical MO calculations (FHMO), to learn more about the nature of the imido bonding in CpNb(NMe)Cl(_2), and compares this class of compound with Group 4 metallocenes (CP2MX2) and complexes of the type Cp*Ta(η(^2)-CHPMe(_2))X(_2). Chapter 4 describes a search for metal-nitrogen complexes exhibiting the unusual phenomenon of bond-stretch isomerism. Modified preparations of molybdenum and tungsten nitrido starting materials have been developed and their reactions with tertiary phosphines examined. Attempts to prepare M(N)Cl(_3)(PMe(_3))(_3) led to the isolation of the phosphiniminato species [Mo(NPMe(_3))Cl(_2)(PMe(_3))(_3)]Cl, which converts under mild conditions to the binuclear nitrido complex [(PMe(_3))(_2)Cl(_3)MoNMoCl(_3)(PMe(_3))(_2)][Me(_3)PNPMe(_3)]. The X-ray structures, reactivity and bonding of these unusual species are discussed. Other attempts to isolate bond-stretch isomers, from tungsten and rhenium nitride starting materials, resulted in nitride complexes such as W(N)Cl(_3)(PR(_3))(_2) (PR(_3) = PMe(_3), PMe(_2)Ph, PPh(_3)) and Re(N)Cl(_2)(PR(_3))(_n) (n = 3, PR(_3) = PMe(_2)Ph; n = 2, PR(_3) = PMePh(_2)). Chapter 5 presents a detailed analysis of the 0x0 bonding in the isomers of Nb(O)Cl(_3)(PMe(_3))(_3) arising by lengthening of the metal-oxygen bond (bond-stretch isomers). The bonding has been analysed over a range of metal-oxygen distances and destabilising anti-bonding interactions found at shorter Nb-O bond lengths. These observations are compared with the results of calculations on the hypothetical nitride species Mo(N)Cl(_3)(PMe(_3))(_3). Chapter 6 gives experimental details for chapter 2-5.
12
Stalder, Sloane Marie. "The synthesis and characterization of some gallophosphates using transition metal complexes as templates." Thesis, Georgia Institute of Technology, 1997. http://hdl.handle.net/1853/27992.
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Gray, Mary Jo. "The synthesis and properties of several aluminophophates templated by chiral transition metal complexes." Thesis, Georgia Institute of Technology, 1997. http://hdl.handle.net/1853/30490.
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Winterborn, D. J. W. "The preparation and chemistry of some trimethylsilyl-substituted cyclopentadienyl group 4 transition-metal and unusual functionalised hydrocarbyl compounds." Thesis, University of Sussex, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.374469.
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Yuan, Yanan. "Oxidative of organic compounds by oxysulfur radicals in the presence of transition metal ions and sulfite." Thesis, Université Clermont Auvergne (2017-2020), 2018. http://www.theses.fr/2018CLFAC052.
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Ces dernières années, de plus en plus de composés organiques réfractaires et toxiques ont été détectés dans les eaux usées. Un bon nombre de ces polluants organiques sont difficilement dégradés par des traitements classiques. Les procédés d’oxydation avancée à base de radicaux sulfates (SR-AOP) sont apparus comme une méthode innovante dans le domaine de la décontamination oxydative des eaux polluées. Des études antérieures ont porté sur ces SR-AOP utilisant du peroxodisulfate (PS) ou du peroxomonosulfate (PMS) comme oxydants, en particulier des couples «métaux de transition et oxydants» (systèmes Fe (II)/PS, systèmes Ni(II)/PMS et Co (II))/PMS), où il a été confirmé que SO4•-·présentent des avantages (sélectivité) par rapport au radical hydroxyle (HO•) pour la décontamination des eaux usées contenant des polluants organiques.Dans cette thèse, nous avons généré des radicaux tels que le radical sulfite SO3•-, le radical sulfate SO4•-, le radical peroxomonosulfate SO5•- à partir d’ions métalliques (Cr(VI), le Co(II), le Fe(III)) capables d’activer le sulfite pour la dégradation des composés organiques. L'efficacité d'élimination et le mécanisme d'oxydation ont été étudiés et le rôle des espèces soufrées a été élucidéIn recent years, more and more refractory and toxic organic compounds are detected in wastewater. Many of these organic pollutants can hardly be degraded by conventional water treatments. Sulfate radical based advanced oxidation process (SR-AOPs), have emerged as a promising method in the field of oxidative decontamination of polluted water. Past studies focused on this SR-AOPs with peroxydisulfate (PS) or peroxymonosulfate (PMS) as oxidants, especially the ‘transition metal + oxidants’ (i.e. Fe(II)/PS system, Ni(II)/PMS system and Co(II)/PMS system), which has been confirmed that SO4·− has advantages over HO in the decontamination of wastewater containing organic pollutants. In this PhD thesis, oxysulfur radicals including sulfite radical SO3·−, sulfate radical SO4·−, peroxymonosulfate radical SO5·− produced by transition metal ions such as Cr(VI), Co(II), Fe(III) activated sulfite were used to degrade organic compounds. The removal efficiency, the oxidation mechanism were examined, and and the role of sulfur species were elucidated
16
Sinlapadech, Sunsanee. "Photoionization of organic molecules in MCM-41, AlMCM-41 and metal containing AlMCM-41 mesoporous materials." online access from Digital Dissertation Consortium, 2003. http://libweb.cityu.edu.hk/cgi-bin/er/db/ddcdiss.pl?3085619.
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Thu, Hung-yat, and 杜鴻溢. "Catalytic C-H bond functionalization reactions catalyzed by rhodium(III) porphyrin, palladium(II) and platinum(II) acetatecomplexes." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B38798268.
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Alías, Rodríguez Marc. "Beyond the static description of the electronic structure:Excited state dynamics in transition metal complexes and organic compounds." Doctoral thesis, Universitat Rovira i Virgili, 2021. http://hdl.handle.net/10803/671956.
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La descripció dels estats excitats és important per racionalitzar processis que succeeixen després d'irradiar amb llum
un material. La comprensió d'aquests estats és una eina fonamental per modificar aquests materials i emprar-los en
diferents funcions. En estudis previs en el nostre grup, la descripció d'aquests estats fou limitada a càlculs estàtics
d'estructura electrònica. En la tesis actual, hem anat un pas més enllà al descriure aquests processos des d'un punt
de vista dinàmic pel que hem utilitzat tres mètodes.
El primer d'ells ha estat la versió depenent del temps de la regla daurada de Fermi per dos complexos de ferro (II).
Aquest mètode ha demostrat ser precís per determinar velocitats i temps de vida per transicions d'entrecreuament
entre estats d'espín diferent en processos relativament ràpids. Tot i això, els resultats obtinguts amb aquesta
metodologia per processos ultraràpids no tenen significat físic. El mecanisme d'aquest procés ultraràpid ha estat
estudiat mitjançant el mètode multi-configuracional depenent del temps emprant productes de Hartree (MCTDH, per
les seves sigles en anglès).(reverse-LIESST, per les seves sigles en anglès) i la població ultraràpida dels triplets en una molècula orgànica com la xantona. Finalment, hem utilitzat les dinàmiques moleculars amb salts entre superfícies. Aquest últim mètode calcula els desplaçaments nuclears a partir dels gradients de la energia electrònica per un estat en particular i els salts entre superfícies són calculats a través d'un algoritme a partir dels acoblaments no adiabàtics. Aquest mètode ha estat utilitzat en el text actual per l'estudi de la reacció de fotoisomerització de l'azobenzè. La descripción de los estados excitados es importante para racionalizar procesos que suceden después de irradiar con luz un material. La comprensión de estos estados es una herramienta importante para modificar materiales con diferentes funcionalidades. En estudios previos en nuestro grupo, la descripción se limitó a cálculos estáticos de la estructura electrónica de estos estados. En la presente tesis, hemos ido un paso más lejos al describir estos procesos desde un punto de vista dinámico a través de tres métodos. El primero de ellos ha sido la versión dependiente del tiempo de la regla dorada de Fermi para dos complejos de hierro (II). Este método ha demostrado ser preciso para determinar velocidades y tiempos de vida para transiciones de entrecruzamiento entre estados de diferente espín en procesos relativamente rápidos. Sin embargo, los resultados obtenidos con este método para procesos ultrarápidos carecen de significado físico. El mecanismo de este proceso ultrarápidos ha sido estudiado mediante el método multi-configuradional dependiente del tiempo a través de productos de Hartree (MCTDH, por sus siglas en inglés).
The description of the excited states is important to rationalize processes happening after irradiation of light. The comprehension of them is an important tool to tune materials for different applications. In previous studies in our group, these descriptions were limited to a static calculation of the electronic structure for the involved states. In this thesis, we have gone one step further to describe these processes from a dynamic point of view through three different methodologies. The first method employed has been the time-dependent Fermi's golden rule in two iron (II) complexes. This method has been proved to accurately determine the intersystem crossing rates and lifetimes in relatively fast processes. However, this gives unphysical rates in the study of an ultra-fast process. This last process is also studied with nuclear quantum dynamics by means of Multi-Configuration time-dependent Hartree (MCTDH). This second methodology needs the creation a priory of a model Hamiltonian and has been used in the reverse-LIESST process of an iron (II) complex and the ultrafast triplet population in xanthone molecule.
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Mapolie, Selwyn Frank. "The synthesis and reactivity of binuclear μ-hydrocarbyl complexes of some transition metals." Doctoral thesis, University of Cape Town, 1988. http://hdl.handle.net/11427/22208.
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The new μ-(l,n)-alkanediyl compounds [(ƞ⁵-C₅R₄Me)Fe(CO)₂ ]₂{μ-(CH₂)n}, (R = H, n = 3 -10 and R =Me, n =3 - 6), [Mn(CO)₅]₂{μ-(CH₂)n} (M = Mn, n = 4-6 and M = Re, n= 3 and 4) have been prepared using essentially two synthetic routes. Thus the iron compounds were synthesized by the reaction of Na[(ƞ⁵-C₅R₄Me)Fe(CO)₂ ] with the appropriate dibromoalkane. The manganese and rhenium compounds on the other hand, were prepared by the decarbonylation of the corresponding diacyl compounds of the type, [M(CO)₅]₂{μ-CO(CH₂)nCO} (M = Mn or Re). These diacyl species in turn were synthesized by the reaction of Na[M(CO)s] with diacyl chlorides. All the new compounds have been fully characterized by microanalysis, infrared, ¹H and ¹³C nmr spectroscopy. The mass spectra of the compounds have been investigated and the fragmentation patterns are discussed and compared with other known polymethylene compounds. An extensive investigation into the reactivity of the new alkanediyl compounds has been carried out. Thus for example the reactivity of the compounds [CpFe(CO)₂]₂{μ-(CH₂)n} with nucleophiles such as tertiary phosphines and isocyanides, yield diacyl compounds of the type [CpFe(CO)L]₂{μ-CO(CH₂)nCO} (Cp = C₅H₄Me or C₅Me₅) and (L = tertiary phosphine or isocyanide). Similar ligand induced CO insertion reactions were observed for the manganese and rhenium alkanediyl compounds. The products from these reactions were characterized using the analytical techniques mentioned earlier. The reactions are discussed and compared with those of mononuclear alkyl compounds of manganese, rhenium and iron. The reactions of some polymethylene bridged compounds with synthesis gas have also been investigated. This reaction is of importance in view of the fact that polymethylene bridged compounds have been implicated in a number of catalytic processes e.g the Fischer- Tropsch reaction. The reaction with synthesis gas was found to yield bifunctional alcohols of the type HO(CH₂)nOH. In a separate study, the binuclear μ-phthaloyl compounds of manganese, rhenium,iron,molybdenum,cobalt and rhodium were prepared and characterized. The phthaloyl compounds of manganese, rhenium and iron were decarbonylated to form the corresponding μ-phenylene compounds. The reactions of some of these compounds with nucleophiles and electrophiles have been studied and the results compared with that of the corresponding mononuclear benzoyl and phenyl compounds.
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Lin, Xufeng. "Density functional theory studies of selected transition metals catalyzed C-C and C-N bond formation reactions." Click to view the E-thesis via HKUTO, 2007. http://sunzi.lib.hku.hk/hkuto/record/B39359645.
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Shaw, Alan. "Synthesis and reactivity studies on oxo and sulphide compounds of the early transition metals." Thesis, Durham University, 1989. http://etheses.dur.ac.uk/6554/.
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This thesis describes studies directed towards the preparation of new oxo compounds of the early transition metals with a view to delineating some of the complex factors which govern their stability and reactivity. For a number of the types of compound studied, the work has also been extended to analogous sulphide systems in order to provide a contrast with another chalcogenide element and further aid an understanding of the bonding and reactivity of both of these elements in a transition metal enviroment. Chapter 1 highlights the areas of transition metal oxo chemistry of relevance to the general theme of the thesis. Chapter 2 describes the use of the commercially available reagents Me(_3)SiYR (R = alkyl, SiMe(_3); Y = O, S), for rapid, convenient, solution syntheses of transition metal oxohalide and sulphidohalide compounds of molybdenum, tungsten, niobium and tantalum. In addition, this methodology allows the preparation of mixed oxosulphidohalide materials and, in certain cases, intermediate alkoxo(siloxo) halide compounds have been isolated. Chapter 3 describes the synthesis, characterisation and reactivity of a series of mononuclear mono-oxo complexes of molybdenum and tungsten including M(O)(OAr)(_4) [M=W, Ar=2,6-Me(_2)C(_6)H(_3) (DMP), 2,4,6-Me(_3)C(_6)H(_2) (TMP), 2,6-Pr(^i)C(_6)H(_3) (DIPP); M=Mo, Ar=(DMP)], M(_2)(O)(_3)(DMP)(_6) and Mo(O)C1(_2)(DMP)(_2). Attempts to synthesise related mononuclear complexes containing the cis di-oxo moeity are also discussed. Chapter 4 describes the synthesis and reactivity of seven coordinate oxo and sulphidohalide derivatives of niobium and tantalum which exhibit the phenomenon of bond-stretch isomerism. Compounds prepared include Nb(O)Br(_3)(PMe(_3))(_3), Nb(S)X(_3)(PMe(_3))(_3) (X=C1, Br) and Ta(S)C1(_3)(PMe(_3))(_3). The latter three have been characterised by X-ray crystallography. Chapter 5 describes the synthesis and reactivity of half-sandwich oxo compounds of niobium and tantalum. Some of the derivatives prepared include[CpNbC1(_3)](_2)(µ(_2)-O), [CpTaC1(_3)](_2)(|µ(_2)-O) and [Cp*TaC1(_3)](_2)(µ(_2)O). The stability of [Cp*Ta(O)Cl(_2)](_2) has been investigated and the X-ray structure of the trinuclear decomposition product Cp*(_3)Ta(_3)O(_4)C1(_4) is described. Chapter 6 describes the use of alkali metal aryloxides as intercalating agents and the preparation of a series of novel intercalation compounds, of the type W(O)(_2)C1(_2)xM (M = Li, Na and K) which display the properties characteristic of tungsten bronzes. Chapter 7 gives experimental details for chapters 2 6.
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El, Assal Z. (Zouhair). "Synthesis and characterization of catalysts for the total oxidation of chlorinated volatile organic compounds." Doctoral thesis, Oulun yliopisto, 2018. http://urn.fi/urn:isbn:9789526221267.
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Abstract The harmful emissions of chlorinated volatile organic compounds (CVOCs) originate only from man-made sources. CVOCs are used in a variety of applications from pharmaceuticals production to decaffeination of coffee. Currently, CVOC emissions are limited by strict legislation. For these reasons, efficient CVOC abatement technologies are required. Catalytic oxidation is very promising option for this purpose, since catalysts can be tailored to each case to maximize the efficiency and minimize the formation of unwanted products, such as dioxins or Cl2. The goal of this thesis was to study the role of the physico-chemical properties of catalysts in dichloromethane (DCM) oxidation. To reach the aim, several catalytic materials were prepared and characterized, and their performance was tested in total oxidation of DCM. The catalytic materials used were powders of four single metal oxides (γ-Al2O3, TiO2, CeO2, MgO), three mixed oxides (Al2O3-xSiO2) washcoated on a cordierite monolith and four active phases (Pt, Cu, V, Mn). At first, support properties were studied. It was found that the DCM conversion and HCl production are dependent on support acidity when the studied single oxides are considered. The best DCM conversions and HCl yields were observed with the support having the highest total acidity (γ-Al2O3). Further, the quality of the by-products formed was dependent on the type of the acid sites present on the support surface. Secondly, the impregnation of the active compound was observed to improve the selectivity of the material. From the tested active phases, Pt presented the best performance, but also V2O5 and CuO showed almost equal performances. Especially CuO supported on γ-Al2O3, that had less formation of by-products and is less toxic than V-containing oxides, seems to be a promising alternative to Pt. Concerning stability, no deactivation was observed after 55h of testing of Pt/Al2O3. Furthermore, in the used reaction conditions, the formation of CuCl2 is not thermodynamically favoured. Finally, the good characteristics of the powder form catalysts were successfully transferred to the monolith. The performance of the Pt/90Al2O3-10SiO2 catalyst in DCM oxidation was improved when the channel density was increased due to an increase in geometric surface area and mechanical integrity factor, and a decrease in open fraction area and thermal integrity factorTiivistelmä Haitallisten kloorattujen orgaanisten yhdisteiden (CVOC) päästöt ovat ihmisten aiheuttamia. CVOC-yhdisteitä käytetään mm. liuottimina lääkeaineiden valmistuksessa ja kofeiinin poistossa. Nykyisin CVOC-päästöjä rajoitetaan tiukalla lainsäädännöllä. Näistä syistä tehokas CVOC-yhdisteiden käsittelymenetelmä on tarpeen. Katalyyttinen hapetus on hyvä vaihtoehto tähän tarkoitukseen, koska katalyytit voidaan räätälöidä niin, että puhdistuksen tehokkuus saadaan maksimoitua samalla kun ei-haluttujen tuotteiden, kuten dioksiinit ja kloorikaasu, muodostuminen voidaan minimoida. Tämän väitöskirjatyön tavoitteena oli selvittää katalyyttien fysikaalis-kemiallisten ominaisuuksien yhteyksiä dikloorimetaanin (DCM) hapetukseen. Tavoitteen saavuttamiseksi valmistettiin useita katalyyttejä, jotka karakterisoitiin ja testattiin DCM:n kokonaishapetuksessa. Työssä tutkittiin neljää jauhemaista metallioksidia (γ-Al2O3, TiO2, CeO2 ja MgO), kolmea metallioksidiseosta (Al2O3-xSiO2), jotka pinnoitettiin kordieriittimonoliitille, sekä neljää aktiivista ainetta: Pt, Cu, V and Mn. Aluksi työssä keskityttiin tukiaineiden ominaisuuksiin. Työn tulokset osoittivat, että DCM:n konversio ja HCl:n tuotanto ovat riippuvaisia tukiaineen happamuudesta. Paras tulos saavutettiin alumiinioksidilla, jolla oli korkein kokonaishappamuus. Lisäksi havaittiin, että sivutuotteiden laatu riippuu tukiaineen pinnalla olevien happopaikkojen tyypistä. Aktiivisen aineen impregnointi tukiaineeseen paransi materiaalin selektiivisyyttä. Tutkituista aineista Pt osoittautui parhaimmaksi, mutta myös V2O5 ja CuO olivat lähes yhtä hyviä. Erityisesti CuO-katalyytti, joka tuotti vähemmän sivutuotteita ja joka on materiaalina vähemmän haitallinen kuin V2O5, osoittautui lupaavaksi jalometallikatalyyttien korvaajaksi. Materiaalien stabiilisuuteen liittyen Pt/Al2O3-katalyytin toiminnassa ei havaittu muutoksia 55 tunnin testauksen jälkeen. Lisäksi CuCl2:n muodostuminen ei mallinnuksen mukaan ole termodynaamisesti todennäköistä tutkituissa reaktio-olosuhteissa. Jauhemaisen katalyytin hyvät ominaisuudet pystyttiin pinnoituksessa siirtämään monoliittirakenteiseen katalyyttiin. Pt/90Al2O3-10SiO2 -katalyytin aktiivisuus DCM:n hapetuksessa tehostui, kun monoliitin aukkoluku kasvoi aiheutuen suuremmasta geometrisestä pinta-alasta ja mekaanisesta eheystekijästä sekä pienemmästä avoimen pinnan osuudesta ja termisestä eheystekijästä
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Allen, Kevin Dale 1968. "Synthesis and characterization of multiple and metallacyclic imido compounds of the early transition metals." Thesis, The University of Arizona, 1992. http://hdl.handle.net/10150/278101.
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The bis(imido) complex Nb(=NAr)₂Cl(py)₂(Ar=2,6-diisopropylphenyl) reacts with two equivalents of LiNHAr in THF to form [Li(THF)₄)][Nb(=NAr)₂(NHAr)₂] (2). Likewise [Nb(NEt₂)₂Cl₃]₂ reacts with excess LiNHAr in THF to form 2. A similar neutral bis(imide) bis(amide) compound (9) of molybdenum has been made. Experiments are presented that suggest the (tris)imido functional group (Nb(=NAr)₃) - arises via an intermolecular deprotonation of [Nb(=NR)₂(NHR)₂]⁻. Complex 2 reacts with 1 equivalent of ᵗBuLi to form the tris(imide) amide [Li₂(THF)₄][Nb(=NAr)₃(NAr)] (6). Ta(OR)₂Cl₃(OEt₂) (OR=2,6-diisopropylphenoxide) reacts with excess 6-methylquinoline (6MQ) to form (η¹-(N)-6MQ)Ta(OR)₂Cl₃ (10). Compound 10 cannot be reduced to the η²-(N,C) product; however, (η₆-C₆Me₆)Ta(OR)₂Cl reacts with excess 6MQ to form (η²-(N,C)-6MQ)Ta(OR)₂Cl(Et₂O) (11), a precursor to metallacyclic imides and a proposed HDN intermediate. Compound 10 can be reduced to afford an unusual Ta(IV) complex (ηˣ-6MQ)Ta(OR)₂Cl₂ (12).
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Bonfield, Eric. "Application of transition metal catalyzed aldehyde-alkyne-amine coupling reactions to tandem reaction sequences: a greener approach to the preparation of useful organic compounds." Thesis, McGill University, 2009. http://digitool.Library.McGill.CA:80/R/?func=dbin-jump-full&object_id=40800.
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Tandem reactions are multiple reactions occurring simultaneously in one-pot, where the product of each reaction is the substrate for the next. The hallmark of tandem reactions is a considerable increase in molecular complexity resulting from a single synthetic step. As this represents a substantial gain in efficiency and step-economy, all tandem reaction methodology represents a more sustainable, “Greener,” approach to preparing more complex organic molecules from simple precursors. The aim of this study was to expand the two-step tandem reaction, aldehyde-alkyne-amine coupling, to include two to three additional intermolecular steps. The goal of green chemistry is for the means to justify the end, but for a proof a principle the end should also justify the means. We chose dipropargyl amines and isoindolines due to their well documented importance as synthetic precursors and biologically active compounds. We outline the development of methodology for the preparation of dipropargyl amines (Chapter 2) and isoindolines (Chapter 3) starting from simple amines, alkynes, and aldehydes in one-pot and a single synthetic operation.Les réactions tandem sont des réactions multiples qui se produisent de façon consécutive dans un seul milieu réactionnel. Le produit de chaque réaction est en fait un réactif pour la réaction suivante. Par le biais des réactions tandem, il est possible d'accéder à des molécules complexes en une seule étape synthétique. Comme elle représente un gain significatif en termes d'efficacité et d'économie synthétique, ce type de réaction représente une approche environnementalement durable pour la préparation de molécules complexes à partir de simples précurseurs.Le but de cette thèse consiste à augmenter la complexité de la réaction tandem entre les aldéhydes, les alcynes et les amines et d'y ajouter d'autres réactifs pour augmenter le nombre d'étapes synthétiques. Le but ultime de la chimie pour le développement durable est pour les moyens de justifier la fin. Par contre, comme preuve de principe, la fin doit aussi justifier les moyens. Nous avons choisi de synthétiser des amines dipropargyliques et des isoindolines en raison de leur importance bien documentée comme précurseurs synthétiques et comme composés biologiquement actifs. La méthodologie pour la préparation des amines dipropargyliques est développée dans le Chapitre 2 alors que la synthèse des isoindolines à partir d'aldéhydes, d'alcynes et d'amines simples (dans un seul milieu réactionnel et en une étape synthétique) est développée dans le Chapitre 3.
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Lin, Xufeng, and 林旭鋒. "Density functional theory studies of selected transition metals catalyzed C-C and C-N bond formation reactions." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2007. http://hub.hku.hk/bib/B39359645.
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Lu, Lihua. "Design and syntheses of Ir(III) complexes as luminescent biosensors." HKBU Institutional Repository, 2015. https://repository.hkbu.edu.hk/etd_oa/276.
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Luminescent transition metal complexes have attracted tremendous interest in the analytical field. Most luminescent metal complexes possess long emission lifetimes in the visible region, and their phosphorescence can be readily distinguished from short-lived background auto-fluorescence. Moreover, their large Stokes shift can prevent self-quenching, while their modular synthesis allows their properties to be readily tuned without labor-intensive synthetic protocols. These properties render transition metal complexes as promising candidates for the development of biosensors. In this study, I aimed to explore different kinds of Ir(III) complexes that can be used as biosensors to monitor DNA secondary structures or protein conformations. Chapter 1 gives a brief introduction regarding the luminescence mechanism of transition metal complexes, and the properties, structures and preparations of Ir(III) complexes are also introduced. Chapters 24 report the syntheses and screening of Ir(III) complexes, and the use of these Ir(III) complexes to monitor the secondary structure of DNA, such as G-quadruplex, G-triplex and i-motif DNA. Chapter 2 reports the G-quadruplex-selective properties of two luminescent Ir(III) complexes 2.1 and 2.9 for the detection of ochratoxin A (OTA) and nicking endonuclease in aqueous solution, respectively; Chapter 3 explores a novel Ir(III) complex 3.8 which is highly specific for G-triplex DNA, and was thus employed for Mung Bean nuclease activity detection; Chapter 4 introduces the Ir(III) complex 4.1 that exhibited a high signal enhancement to i-motif DNA, and was therefore used for terminal deoxynucleotidyl transferase (TdT) activity detection. Chapter 5 describes the two novel cyclometalated Ir(III) complexes 5.1 and 5.21 that were used to monitor two kinds of proteins, human serum albumin (HSA) and beta-amyloid(140) (Aβ140), respectively.
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Vasbinder, Michael John. "Oxidations of organic and inorganic substrates by superoxo-, hydroperoxo-, and oxo-compounds of the transition metals." [Ames, Iowa : Iowa State University], 2006.
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Chen, Haoguo, and 陳浩國. "Silver catalyzed enyne cyclization reactions." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2009. http://hub.hku.hk/bib/B42841409.
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Chen, Haoguo. "Silver catalyzed enyne cyclization reactions." Click to view the E-thesis via HKUTO, 2009. http://sunzi.lib.hku.hk/hkuto/record/B42841409.
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Baker, Schuyler Denton. "Eco-friendly driven remediation of the indoor air environment: the synthesis of novel transition metal doped titania/silica aerogels for degradation of volatile and semi-volatile organic compounds." Thesis, Kansas State University, 2012. http://hdl.handle.net/2097/13348.
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Master of ScienceDepartment of Chemistry
Kenneth Klabunde
Remediation of the indoor environment led to the development of novel catalysts which can absorb light in the visible range. These catalysts were prepared using the wet chemistry method known as sol-gel chemistry because preparation via sol-gel provides a homogeneous gel formation, which can be treated via supercritical drying to produce an aerogel. These aerogels have been found to have high surface areas when a combination of titania/silica is used. The increase in surface area has been shown to enhance the activity of the catalysts. Mixed metal oxide systems were prepared using titanium isopropoxide and tetraethyl orthosilicate to yield a 1:1 system of titania/silica (TiO2/SiO2). These systems were doped during the initial synthesis with transition metals (Mn or Co) to create mixed metal oxide systems which absorb light in the visible light range. These materials were assessed for potential as heterogeneous catalysts via gas-solid phase reactions with acetaldehyde. Degradation of acetaldehyde as well as the formation of CO2 was monitored via gas chromatography-mass spectrometery. To increase the activity, visible light was introduced to the system. Experiments have shown that a 10 mol % manganese doped titania/silica system, in the presence of light, can degrade acetaldehyde. The cobalt doped counterpart showed dark activity in the presence of acetaldehyde resulting in the formation of CO2 without the addition of visible light. In the hope of increasing surface area a mixed solvent (toluene/methanol) synthesis procedure was applied to the manganese doped catalyst. The resulting materials were of a low surface area but showed a significant increase in degradation of acetaldehyde. Examination of the interactions between mixed metal oxide systems and semivolatile organic compounds (SVOCs) was studied. The pollutant, triphenyl phosphate, was dissolved in n-pentane and exposed to 10 mg of a given catalyst. These reactions were monitored using UVVis. All systems but the manganese doped titania/silica system resulted in the observation of no activity with triphenyl phosphate. The manganese doped catalyst shown a peculiar activity, the increase in absorbance of the triphenyl phosphate peaks as well as the formation of a new peak.
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Amenta, Arianna. "Palladium, ruthenium and iron in intramolecular transition metal-catalyzed carbene functionalization reactions of amino-tethered α-diazoesters." Doctoral thesis, Universitat de Barcelona, 2020. http://hdl.handle.net/10803/671148.
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Transition metal-catalyzed intramolecular C–H insertions of diazo compounds represent one of the most elegant and versatile methods in organic synthesis for the construction of carbocyclic and heterocyclic frameworks. In these reactions a C–C bond is formed with high atom economy, with N2 gas being the only subproduct.
In the last years, in the context of a research program aimed at developing efficient methodologies for the synthesis of nitrogen heterocycles, our research group has been studying the transition metal-catalyzed decomposition of amino-tethered α - diazo carbonyl compounds. Specifically, we have reported that palladium catalysts are able to promote the intramolecular carbene C–H insertions to produce pyrrolidines from α-diazoesters, and oxindoles as well as β-lactams from α -diazo- α - (methoxycarbonyl)acetamides.
As a continuation of these studies, in this Thesis we first explored the use of Pd, Rh(II) and Ru(II)-based catalysts for the intramolecular carbene C(sp3)–H insertion of γ - amino-α-diazoesters leading to pyrrolidines. Our comparative study allowed us to identify differences in the reactivities and selectivities between the different transition metals. The results obtained in these annulation reactions show that, although the chemoselectivity of the process is highly substrate-dependent, it can be controlled by adequate catalyst selection.
Taking this work as a reference, we then investigated the use of some structurally diverse Ru(II)-complexes to promote the C(sp3)–H insertion of γ-amino-α-diazoesters to form pyrrolidines. In this context, we have described the first examples of an unprecedented non-metathetic chemistry of Grubbs complexes, which were applied to achieve this target. Moreover, in our preliminary attempts to develop an enantioselective version of this carbene C(sp3)–H insertion reaction, we focused our attention on the use of different chiral Ru(II)-catalysts.
We also investigated the synthesis of tetrahydroquinolines by transition metal- catalyzed intramolecular aromatic CAr(sp2)-H functionalization of γ -anilino α-diazoesters. Both palladium(0)- and Grubbs catalysts were explored for this purpose.
Finally, we broadened our investigation on the transition metal-catalyzed decomposition of amino-tethered diazoesters by exploring the reactions of δ−amino and β-amino α-diazoesters. Some diverse palladium and ruthenium complexes as well as different iron salts were studied.Las reacciones de inserción intramolecular de diazocompuestos en enlaces C–H catalizadas por metales de transición se han convertido en una metodología extraordinariamente versátil para la construcción de sistemas carbocíclicos y heterocíclicos. En estas reacciones, la formación del enlace C–C tiene lugar con una economía atómica considerable ya que se genera N2 gas como único subproducto. Durante los últimos años, como parte de un ambicioso proyecto de investigación enfocado al desarrollo de metodologías más eficientes para la síntesis de heterociclos nitrogenados, en nuestro grupo de investigación se ha estudiado la inserción de carbenos metálicos derivados de compuestos α-diazocarbonilicos en enlaces C–H. En este contexto, se ha demostrado que los catalizadores de paladio pueden promover la inserción intramolecular de carbenos generados a partir de diferentes compuestos α- diazocarbonilicos. En concreto, se ha descrito su utilización en la síntesis de pirrolidinas a partir de α-diazoésteres, y de oxindoles y β-lactamas a partir de α-diazo-α- (metoxycarbonil)acetamidas. Como continuación de estos estudios y con el objetivo de desarrollar una metodología más eficiente para la síntesis de pirrolidinas, en la primera parte de la presente tesis doctoral nos propusimos explorar la viabilidad de diversos complejos de Pd, Rh(II) y Ru(II)como catalizadores en la reacción de inserción en enlaces C(sp3)–H a partir de γ - amino-α-diazoésteres. Este estudio comparativo ha permitido identificar las diferencias de reactividad y selectividad entre los distintos metales de transición. Los resultados obtenidos han puesto de manifiesto que la quimioselectividad de la reacción, aunque es altamente dependiente de la estructura del substrato, puede controlarse mediante una adecuada selección del catalizador. Seguidamente, decidimos explorar la utilización de otros complejos de Ru(II), escogidos en base a su considerable diversidad estructural, como catalizadores de la inserción en enlaces C(sp3)–H a partir de γ -amino-α-diazoésteres. En este contexto, hemos demostrado que los complejos de Grubbs también pueden emplearse para promover la inserción de carbenos en enlaces C(sp3)–H para preparar pirrolidinas. Este trabajo constituye el primer ejemplo de la utilización de este tipo de catalizadores en reacciones de inserción, una transformación química muy distinta de su aplicación clásica en las reacciones de metátesis. En este mismo contexto, hemos realizado también un estudio preliminar encaminado al desarrollo de una versión enantioselectiva de la reacción de inserción, utilizando distintos catalizadores de Ru(II) quirales. Por otro lado, hemos desarrollado un procedimiento para la síntesis de tetrahidroquinolinas mediante la inserción intramolecular de carbenos generados a partir de γ -anilino-α-diazoésteres en enlaces C(sp2)–H aromáticos. Para esta reacción se han explorado tanto los catalizadores de Pd(0) como los complejos de Grubbs. Finalmente, hemos ampliado nuestra investigación acerca de la utilización de distintos metales de transición para promover la descomposición de compuestos α- diazocarbonilicos con el estudio de la reacción a partir de δ-amino- y β-amino-α- diazoésteres. Para ello hemos explorado la utilización de distintos complejos de paladio y rutenio, así como de sales de hierro.
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Åberg, Ola. "Design and Synthesis of 11C-Labelled Compound Libraries for the Molecular Imaging of EGFr, VEGFr-2, AT1 and AT2 Receptors : Transition-Metal Mediated Carbonylations Using [11C]Carbon Monoxide." Doctoral thesis, Uppsala universitet, Institutionen för biokemi och organisk kemi, 2009. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-98599.
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This work deals with radiochemistry and new approaches to develop novel PET tracers labelled with the radionuclide 11C. Two methods for the synthesis of 11C-labelled acrylamides have been explored. First, [1-11C]-acrylic acid was obtained from a palladium(0)-mediated 11C-carboxylation of acetylene with [11C]carbon monoxide; this could be converted to the corresponding acyl chloride and then combined with benzylamine to form N-benzyl[carbonyl-11C]acrylamide. In the second method, the palladium(0)-mediated carbonylation of vinyl halides with [11C]carbon monoxide was explored. This latter method, yielded labelled acrylamides in a single step with retention of configuration at the C=C double bond, and required less amine compared to the acetylene method. The vinyl halide method was used to synthesize a library of 11C-labelled EGFr-inhibitors in 7-61% decay corrected radiochemical yield via a combinatorial approach. The compounds were designed to target either the active or the inactive form of EGFr, following computational docking studies. The rhodium(I)-mediated carbonylative cross-coupling of an azide and an amine was shown to be a very general reaction and was used to synthesize a library of dual VEGFr-2/PDGFrβ inhibitors that were 11C-labelled at the urea position in 38-78% dc rcy. The angiotensin II AT1 receptor antagonist eprosartan was 11C-labelled at one of the carboxyl groups in one step using a palladium(0)-mediated carboxylation. Autoradiography shows specific binding in rat kidney, lung and adrenal cortex, and organ distribution shows a high accumulation in the intestines, kidneys and liver. Specific binding in frozen sections of human adrenal incidentalomas warrants further investigations of this tracer. Three angiotensin II AT2 ligands were 11C-labelled at the amide group in a palladium(0)-mediated aminocarbonylation in 16-36% dc rcy. One of the compounds was evaluated using in vitro using autoradiography, and in vivo using organ distribution and animal PET. The compound was metabolized fast and excreted via urine. High radioactivity was also found in the liver, meaning that more metabolically stable compounds are desirable for future development.
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Bai, Lei. "Cyclodextrins as additives for the synthesis of zirconia-supported metal oxide catalysts for formaldehyde oxidation and extension to the preparation of zirconia." Thesis, Artois, 2013. http://www.theses.fr/2013ARTO0411.
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Les composés organiques volatils comme le formaldéhyde sont des polluants nocifs pour la santé humaine et leur décomposition en composés moins toxiques est fortement étudiée. Ainsi, différents catalyseurs à base d’oxyde métallique permettant une décomposition thermique efficace du formaldéhyde ont été développés. Dans cette optique, les catalyseurs à base d’oxyde métalliques sont souvent présentés comme des catalyseurs prometteurs. Ce travail consiste à préparer des catalyseurs à base de cobalt et/ou de manganèse supportés sur zircone destinés à l’oxydation du formaldéhyde. Les catalyseurs ont été synthétisés par imprégnation en excès de volume (méthode classique) en modifiant la solution métallique par ajout de cyclodextrines.Dans ce travail, différents paramètres tels que le précurseur métallique, la nature de la cyclodextrine et la quantité de cyclodextrines ont été étudiés. Un effet bénéfique de l’ajout de cyclodextrines sur l’activité catalytique est obtenu et le rôle des cyclodextrines lors de chaque étape de la préparation (dans la solution d’imprégnation, avant l’activation et après l’activation) a été abordé. Les interactions entre la cyclodextrine et le précurseur métallique en solution modifient le processus d’activation permettant ainsi la formation de petites particules plus actives.En complément à ce travail, les cyclodextrines ont également été utilisées pour préparer par précipitation assistée une zircone présentant une structure cristalline purement quadratique. La stabilisation de la phase quadratique ayant lieu grâce à la formation d’un précurseur nouveau composé de cyclodextrines incorporées dans le polymère d’oxohydroxyde de zirconium. Cette nouvelle méthode de synthèse a été adaptée pour préparer un oxyde mixte MnOx-ZrO2 qui s’est révélé particulièrement actif dans la réaction d'oxydation du formaldéhydeVolatile organic compounds, such as formaldehyde are currently health concern and their elimination into harmless compounds is of great importance. Different catalysts metal oxides have been developed to decompose formaldehyde under thermal treatments. The present work aims at developing cobalt and/or manganese oxides catalysts supported on zirconia designed for the deep oxidation of formaldehyde. The catalysts have been synthesized by classical wet impregnation method and the started metal solution has been modified by the controlled addition of cyclodextrins.The influence of different parameters, such as the metal precursor, the nature of the cyclodextrin nature and the amount of the cyclodextrin has been studied. A beneficial effect of cyclodextrins addition on the catalytic activity has been obtained and the role of the cyclodextrins at each stage of the preparation has been investigated (i.e. in impregnating solution, before activation and after activation). Interactions occurring in the aqueous phase between the cyclodextrin and the metal precursor modify the activation process leading to the formation of small particles size more active.As an extension, cyclodextrins have also been used to prepare by simple synthesis procedure of single-phase tetragonal zirconia. The stabilization of the tetragonal phase is suggested to occur via the formation of a composite material precursor composed of incorporated cyclodextrin within the polymeric zirconium hydroxide. Finally, the effect of the cyclodextrin modified zirconium hydroxide was adapted in the preparation of a very efficient mixed oxide MnOx-ZrO2 in the oxidation of formaldehyde
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Huang, Yan. "Synthesis, Kinetic and Photocatalytic Studies of Porphyrin-Ruthenium-Oxo Complexes." TopSCHOLAR®, 2010. http://digitalcommons.wku.edu/theses/182.
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Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in Nature, namely the cytochrome P450 enzymes. Ruthenium porphyrin complexes have been the center of the research and have successfully been utilized, as catalysts, in major oxidation reactions such as the hydroxylation of alkanes. This study focuses on kinetic and photocatalytic studies of oxidation reactions with wellcharacterized high-valent ruthenium-oxo porphyrin complexes. The trans-dioxoruthenium(VI) porphyrins have been among the best characterized metal-oxo intermediates and their involvement as the active oxidant in the hydrocarbon oxidation have been extensively studied. Following the literature known methods, a series of trans-dioxoruthenium(VI) porphyrin complexes (3a-b) were synthesized and spectroscopically characterized by UV-vis, IR and lH-NMR. In addition to the well-known chemical methods, we developed a novel photochemical approach for generation of trans-dioxoruthenium(VI) porphyrins with visible light. The fast kinetic study of two-electron oxidations of para-substituted phenyl methyl sulfides by these dioxoruthenium(VI) species was conducted by using stopped-flow spectroscopy. Results showed that the decay of trans--dioxoruthenium(VI) porphyrins in the presence of reactive sulfides follows a biexponential process. The reactivity order in the series of dioxoruthenium complexes follows TPFPP> TPP> TMP, consistent with expectations based on the electrophilic nature of high-valent metal-oxo species. Moreover, the sulfoxidation reactions are 3 to 4 orders of magnitude faster than the well-known epoxidation reactions. In addition, several ruthenium porphyrins were used as the catalysts in the competitive oxidation reactions to identify the kinetically competent oxidants during catalytic turnover conditions. The photocatalytic studies of aerobic oxidation reactions of hydrocarbons catalyzed by a bis-porphyrin-ruthenium(lV) fl-OXO dimer using atmospheric oxygen as oxygen source in the absence of co-reductants were investigated as well. The ruthenium(lV) fl-OXO bisporphyrin (6a) was found to catalyze aerobic oxidation of a variety of organic substrates efficiently. By comparison, 6a was found to be more efficient photocatalyst than the well-known 3a under identical conditions. A KIE at 298K was found to be larger than those observed in autoxidation processes, suggesting a nonradical mechanism that involved the intermediacy of ruthenium(V)-oxo species as postulated.
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Hmimid, Noureddine. "Etude structurale de nouveaux diphosphonates." Grenoble 2 : ANRT, 1986. http://catalogue.bnf.fr/ark:/12148/cb37598321s.
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Abdali, Abdelkrim. "Fonctionnalisation de complexes polyeniques de fer-tricarbonyle : nouvelles voies d'acces aux dienones silylees aux trienes gem-difonctionnels et aux epoxydienes." Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13103.
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Jund, Rodolphe. "Electrochimie de clusters mixtes tetrametalliques." Université Louis Pasteur (Strasbourg) (1971-2008), 1987. http://www.theses.fr/1987STR13175.
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SEMRA, ASSIA. "Substitutions nucleophiles en serie arenetricarbonylchrome." Paris 6, 1987. http://www.theses.fr/1987PA066622.
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Nuel, Didier. "Etude de la reactivite de fragments alkylidynes dans des clusters trinucleaires du fer." Toulouse 3, 1986. http://www.theses.fr/1986TOU30206.
Full textAbstract:
Reactivite des complexes fe::(3)(co)::(9)(cch::(3))(coc::(2)h::(5)) ou fe::(3)(co)::(10)(cch::(3))(h). Les reactions de couplage des groupes alkylidynes avec les algues sont faciles. L'action de co a mis en evidence le couplage reversible dans des conditions douces de 2 fragments alkylidynes. En general, la presence du coordinat hydruro rend les reactions plus complexes
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Iloughmane-Gaspard, Hafida. "Ene reactivite d'alcenylsilanes et -germanes : synthese et stabilisation de metalloles du groupe 14." Toulouse 3, 1986. http://www.theses.fr/1986TOU30214.
Full textAbstract:
La synthese d'alcools allyliques organometalliques du groupe 14 (si,ge) a ete effectuee par oxydation de composes ethyleniques (photo-oxygenation ; epoxydation/rearrangement). Ces alcools ou leurs esters ont ete valorises en tant que precurseurs des premiers metalloles, isologues des cyclopentadienes, c-non substitues ou c-methyles qui ont ete stabilises par complexation-pi (fe,co). L'auteur decrit plus de 100 produits organometalliques nouveaux dont les structures moleculaires sont etablies par spectrometries de resonance magnetique nucleaire, de masse, photo-electronique et de diffraction des rayons x. Les mecanismes des reactions de cycloaddition, d'oxydation et d'elimination mises en jeu au cours de ce travail sont discutes
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Caminade, Anne-Marie. "Stabilisation par complexation d'entites phosphorees de basse coordinence." Toulouse 3, 1988. http://www.theses.fr/1988TOU30073.
Full textAbstract:
On obtient selon le substituant organique du phosphore, des complexes de phosphines, diphosphanes halogenes et de derives phosphores a base coordinence (phosphine, phosphalcine, diphosphine, phosphacumulene
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Sahmoune, Amar. "Extractions synergiques de metaux divalents de transition par association d'une acyl-4-pyrazolone-5 avec des polyethers cycliques et acycliques." Université Louis Pasteur (Strasbourg) (1971-2008), 1988. http://www.theses.fr/1988STR13116.
Full textAbstract:
Extractions de co. Zu. Cd et cu divalents par les melanges phenyl-1 methyl-3 benzoyl-4 pyrazolone-5 ethers crown. La coextraction alcalins-alcalinoterreux complexes par les composes crown et des metaux divalents est possible quand la taille de la cavite de l'ether-crown est voisine de celle de l'alcalin (ou alcalino-terreux) et quand l'ion ml::(3)**(-) est suffisamment stable
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Rouida, Bouchaïb. "Syntheses diastereoselectivites de complexes chiraux du molybdene et du fer carbonyle par action de derives asymetriques du phosphore." Paris 6, 1988. http://www.theses.fr/1988PA066515.
Full textAbstract:
La reaction photochimique de plusieurs phosphines asymetriques avec des complexes carbonyles du fer et du molybdene cyclopentadienyls fournit des complexes chiraux. Ceux-ci se forment par couples de diastereoisomeres en proportions variables. L'effet sterique de ces phosphines sur le mecanisme de reaction est etudie. D'autre part, lorsque le complexe cyclopentadienyl carbonyle du fer comporte une liaison fer-silicium, fer-germanium ou fer-etain il se produit des interactions conduisant a des inductions diastereotopiques importantes
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Navick, Caldentey Martine. "Contribution à l'étude des phénomènes de synergie en extraction liquide-liquide : application à l'extraction du nickel(II) et du cobalt(II) en milieu acide." Paris 6, 1986. http://www.theses.fr/1986PA066297.
Full textAbstract:
Etude des propriétés d'agent d'extraction des acides di(alkyl)dithiophosphoriques ; ils ne peuvent pas être utilisés industriellement car ils s'hydrolysent rapidement au contact d'une phase aqueuse des 35**(o). En fait il semble que les anions di(alkyl) monothiophosphoriques conviennent, utilises en même temps qu'une oxime. Effet de divers facteurs sur la cinétique d'extraction. On peut séparer à ph1, ni et co par une extraction par acide di(ethyl)monothiophosphorique et quinoleinols-8 substitués.
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Conan, Françoise. "Contribution à l'élaboration de nouveaux squelettes organiques via l'étude de la réactivité d'un groupe disulfure de carbone coordine au molybdène." Brest, 1988. http://www.theses.fr/1988BRES2017.
Full textAbstract:
La reactivite du complexe du titre est etudiee vis a vis d'alcynes portant des groupes electroattracteurs. On obtient des complexes metallocycliques a liaison molybdene-carbone ou molybdene-soufre. On prepare un complexe original par addition de trois molecules de propiolonitrile. On etudie egalement la reactivite de ces composes heterocycliques vis a vis de ch::(3)i, nabh::(4) et de hc=c-cn
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Chavant, Pierre Yves. "Reaction de type barbier ou reformatsky effectuees a l'aide de manganese." Paris 6, 1988. http://www.theses.fr/1988PA066138.
Full textAbstract:
Etude de la reactivite du manganese metallique vis-a-vis d'halogenures allyliques et d'halogeno-2 esters. Une etude de l'influence du solvant et de la presence de divers sels metalliques, a debouche sur la mise au point d'une nouvelle voie d'acces a des alcools homoallyliques
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Achi, Sabah Samira. "Nouvelle voie d'acces aux acides alpha -amines, par catalyse homogene a l'aide de complexes de metaux de transition, synthese de nouveaux complexes phosphores chiraux du tungstene pentacarbonyle." Paris 6, 1987. http://www.theses.fr/1987PA066227.
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Menu, Marie-Joëlle. "Nouveaux reactifs dans la chimie des complexes du rhodium, du chrome et du tungstene : les anions diazo rc(n::(2))**(-)." Toulouse 3, 1988. http://www.theses.fr/1988TOU30068.
Full textAbstract:
Synthese des complexes de rh, cr et w contenant le coordinat diazo en faisant reagir les sels de li des anions rc(n::(2))**(-) sur les complexes metalliques. On a isole: (pme::(3))::(4) rhc(n::(2))sime::(3) (pet::(3))::(3) rhc(n::(2))sime::(3), (pme::(3))::(2) rhc(n::(2))(s)p(n-ipr::(2))::(2). On a mis en evidence un complexe carbenique dimere possedant un groupe ylure, lors de la photolyse de (pet::(3))::(3) rhc(n::(2))sime::(3)
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GOMES, DE LIMA LUIS CARLOS. "Reactions d'alcynes cyanes (monocyanoacethylene et dicyanoacethylene), vis-a-vis de complexes organometalliques du fer, du cobalt, du molybdene et du tungstene." Brest, 1986. http://www.theses.fr/1986BRES2009.
Full textAbstract:
Etude de la reactivite de complexes thiolates du fer et du tungstene (cp(co)::(n) m(sch::(3))) vis a vis du mono et du dicyanoacetylene. Aptitude des complexes de co(i) a intervenir dans la formation de molecules organiques. Nature des liaisons m-pb(m=mo ou w) dans les complexes cp(co)::(3)m-pbr::(3) et (cp(co)::(3)m)::(2) pbr::(2). Donnes de rmn de **(95)mo et **(207)pb
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Cromer, Rémy. "Porphyrines n-substituees : modelisation de l'inhibition d'hemoproteines." Université Louis Pasteur (Strasbourg) (1971-2008), 1986. http://www.theses.fr/1986STR13015.
Full textAbstract:
Migration cobalt-azote des groupements : phenyl et styryl. L'etude des reactions de migration dans les porphyrines de cobalt(iii) aryliques a justifie l'utilisation de ces dernieres pour modeliser l'hydrazinolyse des hemoproteines. Les porphyrines de cobalt(iii) aryliques ont un comportement analogue a celui des porphyrines de fer(iii) aryliques. Oxydation des styryl -co(iii) porphyrines. Mecanisme de reaction. Extension de cette reaction a la cyclisation en serie arylique qui permet la synthese de la premiere porphyrine n,n'-(phenylene-1,2) analogue du produit d'inhibition suicide obtenu apres activation de l'amino-1 benzotriazole par divers enzymes a cytochrome p-450