Tri(2-thiophenyl)phosphine (P(C6H4-2-SH)3,PS3) was designed at 1989. Recently chemists use this ligand for enzyme models because it provides rich sulfur environment. Some chemists use PS3 to synthesize novel metal complexes. This thesis deals with the synthesis and structural discussion of germanium and tin complexes bearing PS3 ligands. Reactions with different metal source all yield novel structures. Reaction of GeCl4 with PS3 gives supramolecular structures with continuous £k-£k interaction. Similar reaction with GeCl3Me gives crystals in optically active form in stead of the usual optically inactive racemic form. Reaction with SnCl4 gives six-coordinate dimmeric tin complex (Sn(OMe)(PS3))2 with bridging methoxyl group and thiolate group (from PS3). Reactions using SnCl3Et or SnCl3Bu as metal sources followed by sublimation (140oC , 10-2torr) give reductive elimination products with alkyl groups transferred onto sulfur atom. These two structures are similar in morphology but different in skeletal arrangement.

Tri(2-thiophenyl)phosphine (P(C6H4-2-SH)3, PS3) was designed at 1989. Recently chemists use this ligand for enzyme models because it provides rich sulfur environment. Some chemists use PS3 to synthesize novel metal complexes. Others study the transmetalation of PS3 tin complexes with FeCl3. As a continuation of our long time interest in these tin complexes as alkylation reagents, this thesis reports the synthesis and characterization of the tin-PS3 complexes. Reactions using SnCl3Me or SnCl3Bu as metal sources when dissolved in DMSO gave DMSO adduct of PS3 tin complex while sublimation gave reductive elimination products with alkyl groups transferred onto sulfur atom. The butyl transferred product and its methyl analogous are similar in morphology but different in skeletal arrangement. Reaction of SnCl4 with PS3 gave two different crystals after long standing. One is the hydrolysed product, [Sn(OH)(PS3)]2, with bridging hydroxyl groups and thiolate groups. The other is the product with oxidized ligand. Reaction of SnBr4 with PS3 gave analogous ligand-oxidized product. Reaction of two mole of SnCl3Bu with PS3 resulted in a bimetallic tin complex.

Thesis (M.S.)--University of Missouri, School of Mines and Metallurgy, 1930. / The entire thesis text is included in file. Typescript. Title from title screen of thesis/dissertation PDF file (viewed February 10, 2010) Includes bibliographical references (p. 63-64).

ITC/USA 2013 Conference Proceedings / The Forty-Ninth Annual International Telemetering Conference and Technical Exhibition / October 21-24, 2013 / Bally's Hotel & Convention Center, Las Vegas, NV / The need for increased downlink data rates and bandwidth for Earth Observation (EO) missions is driving mission planners to consider Ka-Band (25.5 to 27.0 GHz) downlinks to replace or augment the existing X-Band (8.025 to 8.400 GHz) services. Future ground stations will be required to support both bands as well as S-Band (2.0-2.3) GHz telemetry and command functions. This paper discusses the inherent tradeoffs in such a design, and proposes an implementation which permits simultaneous data reception in X-Band and Ka-Band, while providing TT&C functionality at S-Band. Analytical and measured data for the implementation are provided.

Important reactions are catalyzed by enzymes employing polynuclear cofactors, often characterized by weak-field ligands and transition metal ions within the sum of the van der Waals radii. While the overall stoichiometries and, in many cases, the structures, of the cofactors are known, the roles of the individual metal ions remain uncertain. Our approach is to investigate model clusters stabilized by a hexadentate, trinucleating ligand. The hexaamine ligand \((MeC (CH_2NHC_6H_4-o-NHPh)_3) (^{Ph}LH_6)\) allows facile synthesis of the clusters \((^{Ph}L)Fe_3(thf)_3\), \((^{Ph}L)Fe_3 (py)_3\), and \((^{Ph}L)Fe_3(PMe_2Ph)_3\) (thf = tetrahydrofuran, py = pyridine). The phenyl substituents on the ligand sterically prevent strong M–M bonding, but permit weaker M–M orbital interactions, with Fe–Fe distances near those found in Fe metal. The complex \((^{Ph}L)Fe_3(thf)_3\) exhibits a well-isolated S = 5 or S = 6 ground state over 5 - 300 K, as evidenced by magnetic susceptibility and reduced magnetization data. However, in the stronger-field pyridine and phosphine complexes, temperature dependent susceptibility is observed which is best modeled as a spin state transition from S = 2 to S = 4. Variable-temperature crystallography and Mössbauer spectroscopy reveal a whole-molecule, rather than site-isolated, spin transition. The all-ferrous cluster \((^{Ph}L)Fe_3(thf)_3\) can be oxidized with triphenylmethyl halides or iodine to give singly-oxidized clusters of the form \((^{Ph}L)Fe_3X(L)\) and \([(^{Ph}L)Fe_3(\mu-X)]_2 (X = Cl, Br, I; L = thf, py)\), in which one Fe–Fe distance contracts to 2.30 Å and the others lengthen to 2.6-2.7 Å. The halide and solvent ligands coordinate a unique Fe, but Mössbauer spectroscopy shows that the diiron pair bears the oxidation. Magnetic data can be modeled by considering a high-spin ferrous ion ferromagnetically coupled to an \(S = 3/2 [Fe_2]^{5+}\) unit. When \([(^{Ph}L)Fe_3(\mu-Cl)]_2\) is reacted with two or five equivalents of \(CoCl_2\) in tetrahydrofuran, the fully-substituted complexes \((^{Ph}L)Fe_2CoCl(acn)\) and \((^{Ph}L)FeCo_2Cl(acn)\) (acn = acetonitrile) can be isolated. \(^1H\) nuclear magnetic resonance shows that they are distinct species, not a mixture, and the elemental ratios are confirmed by X-ray fluorescence spectroscopy. Mössbauer spectroscopy shows that the Co preferentially substitutes into the \([M_2]^{5+}\) unit, as the ferrous site doublet is completely absent in \((^{Ph}L)FeCo_2Cl(acn)\). / Chemistry and Chemical Biology

La recherche sur la synthèse Fischer-Tropsch (FTS) a depuis 20 ans été fortement stimulée par la demande d’énergie croissante. Le projet de ce doctorat vise à élaborer un catalyseur nanométrique hétérogène sans porosité interne qui sera utilisé avec du gaz de synthèse produit par gazéification sous air de matières renouvelables. Les objectifs principaux consistent à valider un protocole de fabrication du catalyseur par plasma, optimiser les conditions d’opération, comparer avec une option commerciale, évaluer le potentiel des additifs et concevoir un modèle cinétique. Le catalyseur est constitué de nanoparticules de carbure de fer encapsulées dans du carbone devant être au moins partiellement enlevé avant la réaction. Un réacteur a été conçu et les conditions optimales ont été estimées à : • température inférieure à 250°C pour limiter la réaction de conversion du gaz à l’eau (water-gas-shift; WGS) tout en maintenant une activité optimale pour la FTS; • pression supérieure à 15 bars pour assurer que le milieu liquide de la réaction soit saturé en réactifs, mais inférieure à 25 bars pour permettre l’évacuation de l’eau; • une vitesse spatiale de 1 200 ml[indice inférieur gaz]/(h*g[indice inférieur cata]) qui assure une conversion maximale aux autres conditions optimisées. Du Nanocat, un matériel commercial constitué de nanoparticules d’hématite non-supportées, a été utilisé comme matériel de référence. Il doit toutefois être transformé en carbure de fer par une réaction avec du CO. Dans le système de réaction et les conditions testées, les performances du Nanocat sont très similaires à celle du catalyseur produit par plasma. Du Cu et du K ont été utilisés comme dopants du catalyseur; le dopage est simultané à la fabrication du catalyseur. Une conversion complète et sans désactivation a été obtenue, mais l’étendue de la réaction WGS a été multipliée par 3. Ce dopage s’est avéré bénéfique mais une optimisation de la charge est requise. Le modèle choisi pour simuler la FTS est basé sur une cinétique phénoménologique : les paramètres de la réaction sont réunis en un facteur mis en fonction d’une réponse du système réactionnel. La prédiction du modèle phénoménologique est bonne pour la conversion du CO et pour la WGS, mais pas pour la conversion FTS; il donne aussi de bons résultats avec des données de la littérature.

Th. doct.--Électronique et communications--Paris--ENST, 1991. / Notes bibliogr. Résumés en français et en anglais.

Thesis (Professional Degree)--University of Missouri, School of Mines and Metallurgy, 1939. / The entire thesis text is included in file. Typescript. Title from title screen of thesis/dissertation PDF file (viewed March 22, 2010)

Universiẗat, Diss., 2000--München.

Universiẗat, Diss., 2001--München.