INORGANIC CHEMISTRY

Author: MEDINA MUÑOZ MANUELA ELOÍSA.
Year: 2003.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: ICMM (CSIC) Y UNIVERSIDAD COMPLUTENSE DE MADRID.

Summary: Have been obtained by synthesis hydro or solvotermal monocrystals seven new compounds microporosos formulas: (NH4) 3Al (PO4) 2, (I), (NH4) 2-x (H3O) xAl2 (PO4) 2 (OH) 2, ( II) Ge16O32 (OH) (C6H12N2H) .1.125 H2O (ICMM5); Ge9O19 (OH) 2 (enH2) 2 (in) 0.5H2O (ICMM6); Ge13O26 (OH) 4 [C6N2H8] 2 2 + (H2O) 2.5 (ICMM7) and [Zn (C17H8F6O4)], (Zn1), in addition to two complexes germanium formula: [Ge (IV) (OH) 6] 2-[Ge (II) (at) 3] 2 + and [Ge (IV) (N2H2C2H4) 3] 2-[Ge (II) (at) 3] 2 +. For all the reaction has been optimized synthesis process by changing the variables that determine what, until obtaining pure compounds for use in catalytic tests, it has determindo the crystalline structure of these compounds by X-ray diffraction in monocristal. The three aluminofosfatos anionic microporosos were obtained by changing the ratio Al / P. Resultando a composite laminate (R) consisting of tetrahedra phosphorus and aluminum, with channels 4R and 12R and two dimensional compounds (II) and (III); with frameworks and polyhedra formed by different types of channels; tetrahedra phosphorus and bipirámides trigonales and octaedros aluminum channels 8R and some of 5R for (II), and in the case of (III) tetrahedra phosphorus and bipirámides trigonales aluminum, ancales 4R, 8R and 12R. It has established a structural relationship between the three compounds according to the ratio Al / P. With the two aluminosfosfatos dimensional tests have been performed confirming its catalytic activity in reactions acilación of Friedel-Crafts and acetalización. These two aluminofosfatos are stable and can be recovered and reused in at least four successive catalytic cycles without losing their structure or their activities. The three germanatos microporosos: ICMM5, ICMM6 and ICMM7 have been obtained by synthesis hydro or solvotermal using different amines symmetrical and asymmetrical: [1,4-diazabiciclo- [2,2,2] -octanol] (DABCO), ethylene diamine ( in) and 4-aminoetilpiperazina. ICMM5 is a germanato microporoso dimensional, consisting of germanium and tetrahedra with a three-dimensional system of channels 12R, the same size and perpendicular to each other. The effect has been observed cooperative director of ions (OH) - and cations dabconio + polymerised in training zeotipo ICMM5. It postulates that in the initial steps of training zeotipo, the group hiroxilo induces the formation of tetrámeros Ge4O8 (OH) -, which in turn exert an effect of anion template similar to that commonly played in the formation of structures organic cations (cations dabconio in ICMM5). The existence of these tetrámeros, along with the distribution of cations dabconiio + polymerised prevents this zeotipo can be seen as a superstructure 2x2 of the zeolite beta. In addition it has been shown the character bifuncional this germanato in organic reactions catalyzed by acids and bases. ICMM6 is a zeotipo chiral with space group C222 1, consisting of tetrahedra, bipirámides trigonales and octaedros germanium and one-dimensional helical interconnected channels of 8R, 11R and 11R. It has confirmed the presence of the same enantiomorfo in different crystals studied. ICMM6 is a material chiral bifuncional (acid) to various organic reactions studied; stable in water and organic solvents that can be recovered and reused in successive cycles without losing their catalytic activity. ICMM7 was obtained using an asymmetric amine (4-aminoetilpiperazina). It is a zeotipo dimensional formed from tetrahedra and ocatedros germanium and channels 6R, 8R, 12R and 14R. Its structure with 10 +3 SBUs, distributed in three layers of polyhedra (4 O + 6 Td + 3 Td) can be associated with the ore farmacosiderita units 10SBUs, but with different management concerning leading to a new structure very open. In an effort to explore and 8 studiar 7c7 factors affecting the formation of ICMM6 have been detained different reactions at different stages crystals isolated two compounds coordination catión - anión de germanium: [Ge (IV) (OH) 6 Ge] 2-[(II) (at) 3] 2 + and [Ge (IV) (N2H2C2H4) 3] 2-[Ge (II) (at) 3] 2 +, noting that they are also chiral. This raises the possibility that these processes quiralidad formation, which appears likely the transfer of the same from the complex framework, it can act as a mere template or as the initiator in the formation of frmework, disappearing completely at the end of the reaction having formed the entire final product of the same. Applying the methodology of our gurpo investigation has begun studying polymeric materials organo-inorgánicos to obtain materials pore size larger or even nanoporosos and seeking cooperative effect of metal and organic connectors. It has obtained a complex chiral polymer organo-inorganico zinc formula [Zn (C17H8F6O4)] channels and hidrofilicos and hydrophobic properties of absorption. It has tested its catalytic activity to see the ability of chiral recognition in reactions acetalización of (R, S) -2-fenil propionaldehido.

Author: LÒDERS ULRIKE ANNE.
Year: 2004.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: ESCUELA DE POSTGRADO.

Summary: This report describes the growth, spray cathodic rf of thin layers of NiFe2O4 and CoCr2O4 on various substrates and the subsequent magnetic and electrical characterization. The goal is to integrate these layers in devices magnetoelectrónicos such as unions or tunnel filters spin. We discovered that the growth epitaxial stabilizes new phases oxide NiFe2O4 who have remarkably different properties. As such a dramatic increase of the magnetization or the ability to drastically alter its transport properties, can obtain conductive or insulating layers. We argue that increasing the magnetization is due to the stabilization of a phase NiFe2O4 spinel which is partially reverse, in which ions Ni2 + are distributed between the two positions available (tetrahedral and octaédrica) of the structure. The introduction of additional oxygen vacancy is probably the cause of the existence of an electronic configuration mixed Fe2 + / 3 + in the subnet octaédrica. The conductive layers of NiFe2O4 were used as electrodes ferrimagnéticos metal joints in the tunnel. It has been possible to measure a magnetoresistencia tunnel important to temperatures as high as 280K. The values of mangetoresistencia correspond to a spin polarization of NiFe2O4 of approximately 40%, which is almost independent of temperature. These results suggest that the new phase conductive we have stabilized is a candidate as a source is interesting spin polarized. Moreover, the NiFe2O4 granting asylum have been implemented, for the first time, as a tunnel barrier in a heteroestructura filter spin. We have seen a magnetorresistencia tunnel that reaches values of up to 50%. On the basis of these measures we have deducted relevant details of the electronic structure of partially reverse phase of NiFe2O4. We have grown oxide CoCr2O4 on different substrates, such as MgO (001) and MgAl2O4 (001). We note that this oxide presents a remarkable trend growth 3D. The study detalado effect of the parameters of growth has enabled us to on the one hand, which is to elucidate the mechanisms leading to self-organization so perfect and the other to determine that, in the right conditions, can be obtained templates totally facteados with multiple possibilities for future apliaciones.

Author: CRUZ YUSTA MANUEL.
Year: 2004.
University: CÓRDOBA.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This mamoria has implemented a technique of crafting sheets of low cost as the spray pyrolysis for the preparation of thin electrode material differences likely to be transformed into dioxide lead to its implementation in lead acid batteries. Among other things, the merits of the spray pyrolysis technique are such easy control of the thickness or overlapping layers of different materials and their relative ease to be applied in a manufacturing line also allows work with both solutions with emulsions. As starting materials in the preparation of electrodes was used lead acetate (II) when working with solutions and 4BS, pasta and green PbO2 in the case of emulsions. In the case of lead acetate (II) 4BS and green pasta, we found a good retention capacity around the 120 Ah / kg, values similar to those described in the literature for electrodes prepared with these materials using conventional methods such as doughy. In contrast to the case of lead dioxide was found an increased capacity to 160 Ah / kg. After characterizing this compound through various techniques such as SEM, TEM, BET, or IGT XRD, we have concluded that the increased capacity that is able to liberate this compound is due to the large amount of water present in this sample (about 4%) along with the small particle size that presents this lead dioxide (about 15-20nm).

Author: KRSTIC VESNA.
Year: 2004.
University: CANTABRIA.
Place of defense: E.T.S. ING. INDUSTRIALES Y TELECOMUNICACION.
Place of preparation: E.T.S. ING. INDUSTRIALES Y TELECOMUNICACION.

Summary: Have been synthesized and caracterizdo catalysts Rh-soportdo (alone or promoted Sn), using different types of media. As carriers catalysts were used both material microporosos: silicates laminar (bentonites) from different origins, and bentonites modified by the introduction of pillars (PILC's) or processed into products zeolíticos; materials mesoporosos as MCM-41, with one or two sources of Silicon. These catalysts have been used in the hydrogenation of crotonaldehído in gas phase and soft conditions, high interest both in academic and industrial fine chemicals, pharmaceuticals and food. It has been analyzed and discussed the activity / selectivity in relation to the characteristics of different media and different working conditions such as temperature reduction Rh, reaction temperatures and the presence of tin as a promoter. It has been characterized by different catalysts instrumental techniques UV-Vis, IR spectroscopy, IGT / DTG, XRD, isotherms of adsorción - desorción of N2, quimisorción of O2/H2, quimisorción of NH3, adsorption, desorption of pyridine through espectrospocpía IR-TF , and XPS was used gas chromatography for the hydrogenation of crotonaldehído. The results show that both the clay starting as amended (with pillars or converted into zeolites) and materials MCM-41, carriers have proved suitable for the formation of ctalizadores heterogeneous Rh and Rh promoted Sn, having generated, therefore, new materials with high added value in the case of modified clays and new challenges for the implementation of new nanomaterials MCM-41. It is also noted that the addition of Sn as a promoter, amending the conversation at all temperatures reaction obtained for all catalysts, greater selectivity toward alcohol crolítico that in the absence of Sn. In short, in the course of this work have been able to develop catalysts that show generally high selectivity toward alcohol crotílico in hydrogenation of crotonaldehído, condicones soft and atmospheric pressure, condicones usual work in the fine chemicals industry, pharmaceutical and food , where it has the greatest impact the implementation of the reaction studied.

Author: HUNGRÍA HERNÁNDEZ M. TERESA.
Year: 2004.
University: AUTÓNOMA DE MADRID.
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The work of the doctoral thesis has focused on the development of an improved method of synthesis (activation mecanoquímica), the structural characterization, processing and the study of certain properties of materials based on the structure perovskita, placing a special emphasis on oxides applied in the field of electrocerámicas. The route of synthesis based on the activation mecanoquímica, tuning to obtain stages type perovskita both laminar, in the case of the family Ruddlesden-Popper - Sr2 [Srn-1TinO3n +1] -, and three-dimensional, in the case of Sr1 - xBaxTiO3 and NaNbO3, represents a considerable saving of time and energy in obtaining the compounds studied, as well as enhance sinterizabilidad of precursors of ceramic materials, as has been evident especially in the case of material antiferroeléctrico NaNbO3. The activation mecanoquímica is an interesting alternative to ceramic method, which consists in subjecting a mixture of reagents to a grinding strong, which increases the uniformity of the sample, in addition to the sound generated from a field of deformation which leads to increased the same power, the accumulation of defects and the total or partial destruction of crystalline order may amorphous products obtained relatively easily. Thus there is the decline in the size of particles in the mixture of departure and a significant increase in reactivity, disminuyéndose and the energy barrier needed to produce certain chemical reactions. The products obtained through the use of the route based on the activation mecanoquímica, have been structurally characterized both by X-ray diffraction room temperature and temperatures rising, and by electron microscopy and takes place the morphological characterization by mícroscopía scanning electron (SEM ) and structural characterization help of the local high-resolution electron microscopy (HREM) and electron diffraction. Once you have conducted the synthesis of precursor powder, is made up of the same and then sintering. The last two stages are provided if it was a precursor of small particle size and high reactivity, conditions are satisfied with precursors obtained through activation mecanoquímica. It has made a comparative study of processing methods are as diverse as: conventional sintering, hot pressing and spark plasma sintering. In the conventional sintering, the ceramic once formed is subjected to a heating process, generating a much larger grain size of the higher processing temperature. One way to improve the density, inhibiting excessive growth of grain, is to apply pressure simultaneous warming, such as processing by pressing hot or hot-pressing, which get densídades high temperatures lower than sintered required in the classic, besides controlling the resulting grain size. In the case of the use of spark plasma sintering, the sample is subjected to the combined effect of temperature and pressure, as in the hot-pressed, but in this case the sample, placed on a bed of graphite, suffers the action of a electric current press. This is a process that allows a very rapid warming, "which is very high densities can be achieved in just a few minutes. Electrical characterization of materials with high density obtained for the different compositions studied, and has a great interest it serves to study the variation of the properties depending on many factors such as composition, the method of synthesis and processing.

Author: POZAS BRAVO RAÚL.
Year: 2004.
University: SEVILLA.
Place of defense: CENTRO DE INVESTIGACIONES CIENTÍFICAS ISLA DE LA CARTUJA.
Place of preparation: INSTITUTO DE CIENCIA DE MATERIALES DE SEVILLA (CSIC-UNIVERSIDAD DE SEVILLA).

Summary: The fundamental objective of this work is to obtain nanoparticles aciculares of Fe-Co smaller than those that can encontrare in the scientific literature (length increased 170 nm) and narrow size distribution, with a high degree of morphological and microstructural control , high magnetic properties (high values of coercitivida, squaring the hysteresis curve and mangetización saturation) and stable compared to oxidation. This objective has been addressed through various stages: A-Developing a method for synthesis of nanoparticles aciculares goetita with size (about 100 nm) and uniform manner, based on oxidation by bubbling air solutions FeSO4 previously precipitated by the addition of Na2CO3. B-Optimizing protection from siterización of these precursors by coating or doped with aluminum oxide or yttrium. C-Optimizing the method of incorporation of C in these precursors, as the amount built, analyzing the impact the nature and distribution of species in the Co nanoparticles aciculares Faith finally obtained on its magnetic properties.

Author: BELEÑA POZO IRENE.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: INSTITUTO TECNOLÓGICO DE LA CONSTRUCCIÓN DE VALENCIA.

Summary: The materials geopoliméricos are polymers, inorganic flame retardants since the early 70 have been studied and developed for many applications, because of its excellent mechanical properties, high temperature resistance and durability. This thesis has been developed materials geopoliméricos sustainable, with good mechanical properties for use as building materials and low-cost, based on the reuse of various industrial waste from various sources to lower costs and make them competitive with building materials traditional. This has been further developed in the study of the influence of various experimental parameters in the structure, microstructure and mechanical properties, as well as various aspects of the kinetic reaction geopolimerización. The parameters studied were the relations molars SiO2/Al2O3 and H2O/Na2O, the nature of the cation (Na +, K +) and the temperature curing and drying. Structural changes are followed mainly by MAS-NMR and XRD, using other techniques to support the MEB and DSC. The mechanical properties have been studied resistance to understanding and microdureza and Vickers. There have also been optimized processing parameters in the manufacture of tiles geopoliméricas through a process of vibro-comprensión and from mtacaolín as a source of Al and Si, and partial replacement of it by waste oil catalytic cracking or red sludge generated the Bayer process of obtaining alumina from bauxista. We have optimized dosages and prototypes were manufactured tile, characterize their mechanical properties based on specific rules of concrete tile. There have been tiles from this waste and have been found to comply with specific concrete tile. There have been tiles Since these wastes and has been found to comply with technical specifications proposed in the legislation for concrete tiles, their faeces potentially cost competitive compared to similar products on the market.

Author: PRESA SOTO ALEJANDRO.
Year: 2005.
University: OVIEDO.
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA.

Summary: In order to evaluate the catalytic activity enantioselectiva centers located in the "pockets chiral" containing polifosfacenos units R-2, 2Â'-dioxi-1, 1Â'-binaftil, has developed the synthesis of polymeric complex linear or entrecruzados formed by the coordination of fragments of type [Ru (II) (p-cimeno)] (neutral or cationic) on the groups binders of polibinaftoxifosfacenos chiral overall composition of ([NP (O2C20H12)] 1-x [N (ENT) 2] x) (0.1 less than x less than 0.2 L = P, PPh2) or ([NP (O2C20H10-F2)] 0.8 [N (O-C6H4-PPh2) 2] 0.2), F = Br, SiMe3 , SiPhMe2, SiPh2Me, SiPh4, SnMe3 and SnPh3, located in the positions 6.6 Â 'binaftilo. They have synthesized new polifosfacenos copolymers groups with R-2, 2Â'-dioxi-, 1.1 Â'-binaftil and has been succeeded by his chemical funcionalización direct derivation on the positions 6.6 Â 'binaftilo. The polifosfacenos preparations are optically active and have been completely characterized, found that dissolution presented helical structures with a sense of preferential propeller distributed along the chains, and in the solid state are mesomórficos structure esméctica with a separation between planes that varies systematically according to the substituted. Its stability configuracional is very high because only experienced processes atropisomerización in the vicinity of the glass transition temperature (about 300Â ° C). The complex preparations were very active as a catalyst in the transfer of hydrogen from isopropanol and acetophenone, but in no case was observed enantioselectividad, so it can be concluded that the "pocket chirality 'is not estereoquímicamente active in this reaction. In order to develop a new model of catalyst have been synthesized other polifosfacenos optically active carriers of groups PPh2 located in the positions 6.6 Â 'of binaftilo of general formula ([NP (O2C20H10 (PPh2) 2] 0.1 [NP (O2C12H8)] 0.9) n.

Author: SILVA SANCHEZ IVAN DA.
Year: 2005.
University: OVIEDO.
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA.

Summary: This report describes the synthesis and structural characterization of complex trinucleares of ruthenium and osmium and ruthenium with mononuclear ligands chiral N-dadores. The ligands used are compounds atropisoméricos 2.2 Â'-diamino-1, 1Â'-binaftaleno and N, N'-bis (6-metil-2-piridil) -1.2 -diaminociclohexano and also ligands possessing one or more centers estereogénicos such as: 2-amino-4-fenil- (4R) -2-oxazolina, indanil-2- (2'-aminofenil) - (4R, 5S) -2-oxazolina, indanil-2-amino- ( 4 R, 5S) -2-oxazolina, 2,3,5,6-tetrahidro-6-fenil- (6R) -imidazo [2,1-b] thiazole and derived from the latter. Finally, it describes a study of catalytic asymmetric transfer reactions of hydrogen and ketones reactions Diels-Alder asymmetrical in which they are used as precursors catalytic complexes and tri mononuclear ruthenium described above.

Author: GÓMEZ RODRÍGUEZ M. LOURDES.
Year: 2005.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: We carried out the synthesis of acid 5-acetibarbitúrico and, from it, were synthesized six tiosemicarbazonas which were characterized using various techniques espectrocópicas. He then became salts react with nickel, palladium, platinum, copper, zinc and cadmium, obtaining a series of metal complexes were characterized using the same techniques. Finally, we performed a study of the biological activity of the palace complexes and platinum, with the cell line Hela-229 (carcinoma of the cervix human).

Author: FERREIRA BAPTISTA LOPES.
Year: 2005.
University: POLITÉCNICA DE MADRID.
Place of defense: ETS INGENIEROS DE MINAS.
Place of preparation: ETS INGENIEROS DE MINAS.

Summary: This thesis has done a thorough study of the environment that is the city of Luanda and its environs, starting by establishing a methodology capable of enabling knowledge of the characteristics of the medium as a whole, taking into account the processes that occur there and the activities in their environment. The work consisted primarily of determining the physicochemical properties of three means their materials particulate dust, soil and sediments (of coastline and rivers of the city). To that end, have been analyzed a total of 222 samples, with 92 of urban dust, 63 sediment coast, 10 sediment from streams and 57 soil or geological formations around the city. Have been identified mainly physical and physico-chemical properties such as soil texture, pH, electrical conductivity, the percentage of organic matter, the percentage of oxihidróxidos iron and manganese, the percentage of carbonates and the content of 35 elements chemicals including some relevant environment. The set of properties we have studied to characterize the environment and the media studied, but one of the approaches that has deepened with care and detail is in relation to the different behavior of certain chemical elements in the three materials and in the middle urban in particular. Hence, it has been possible to show that trace elements in urban areas are subject to the same physical and chemical processes that take place in the natural environment. Thus, it has been able to study their behavior using models and tools similar to those that have traditionally been used for the study of natural systems and resources. The data obtained have shown that dust from the city of Luanda has a composition which depends crucially on processes of natural origin, characterized by relatively low content in metals and trace elements in relation to other urban environments of most developed cities, but with values moderately high for Pb and Zn. It also has been observed, perhaps due to the large contribution from natural sources, is a carbonated accentuated and relative homogeneity in its spatial variability. In relation to the coast, the different properties selected, presented a variation fluctuating, due primarily to two criteria: the difference lithological along the coast and the intensity or the provision of materials from the city (anthropogenic activity). It has been noted above that the bay is one of the areas of the coast most impacted by human activity as reflected by the high content of heavy metals accumulating sediments with its special relevance for Ag, Cu, Pb and Zn , and which have been shown to be superior to the values usually considered optimal and consistent means for marine and aquatic life. It has been interesting to observe mainly in the city is the main source of trace elements in sediments both as a stream of coastline. Finally, through a study applied to the evaluation of risk exposure to dust poses to children in Luanda, it has been determined that the trace elements which pose a higher health risk are arsenic and lead, and that ingestion of particles is the path of greatest risk for almost all elements considered. This reinforces the suspicion and wide the likelihood that children can suffer adverse effects because of some elements in the habit of carrying non-food items in their mouths involves ingesting greater amounts of dust and consequently higher content of toxic. This Teis has relizado or 8 No thorough study 924 or environment that is the city of Luanda and its environs, starting by establishing a methodology capable of enabling knowledge of the characteristics of the medium as a whole, taking into account the processes Hence occur and the activities in their environment. The work consisted primarily of identifying the physico-chemical properties of three means their materials particulate dust, soil and sediments (of coastline and rivers of the city). For the purpose. Have analyzed a total of 222 samples, with 92 of urban dust, 63 sediment coast, 10 of sedimenetos of streams and 57 soil or formations geólogicas environment of the city. Have been identified mainly physical properties and físico-quimicas as the texture of the soil, pH, electrical conductivity, the percentage in organic matter, the percentage of oxihidróxidos of hierra and manganese, the percentage of carbonates and the content of 35 elements chemicals including some relevant environment. The set of properties we have studied to characterize the environment and the media studied, but one of the approaches that has deepened with care and detail is in relation to the different behavior of certain chemical elements in the three materials and deepened with care and detail is in relation to the different behavior of certain chemical elements in the three materials and in urban areas in particular. Hence, it has been possible to show that trace elements in urban areas are subjected to the same processes físico-quimicos taking place in the natural environment.

Author: CUESTA ORCOYEN LUCIANO.
Year: 2005.
University: OVIEDO.
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA.

Summary: The first chapter of this thesis includes the synthesis of new fluorocomplejo [Mo (3-metalilo) F (CO) 2 (NN)] (NN = 1,10-fenantrolina) prepared in high yield and a cleaner way, that is as a single product by the reaction of the precursor [Mo (3-metalilo) (OTf) (CO) 2 (NN)] (in turn obtained by reaction of [Mo (3-metalilo) Cl (CO) 2 (NN )] with triflato silver) with fluoride tetrabutilamonio. The fluorocomplejo was dominated completely, both in solid form as dissolution, and was used for the synthesis of rational compounds binucleares both homobimetálicos as heterobimetálicos. It should be noted that these results have shown, as these compounds binucleares have no union between two metal fragments over the bridge fluoride, the fluorocomplejo mentioned is a good metaloligando. In the second chapter of this work are reflected new contributions to the study of the chemistry of complex hidroxo of metal fragments Mo (3-alilo) (CO) 2 (NN) and Re (CO) 3 (NN), being an NN diimina aromatic as 2.2 '-bipiridina or 1,10-fenantrolina. Specifically, have studied the reactions of these complexes hidroxo face esters, isocyanates, isothiocyanates, acetilenos activated (acetilendicarboxilato Dimethyl and propiolato methyl), cetenas, Maleic anhydride and lactidas. The products obtained indicate that the ligand OH complex hidroxo serving as nucleófilo in all cases. In addition to the characterization espectroscópica, using infrared and nuclear magnetic resonance of 1H and 13C, at least one of the products of each type of reaction has been characterized by X-ray diffraction In some cases, has been carried out desmetalación of organic ligand resulting acid tríflico or triflato methyl. The third section presents the synthesis and characterization of compounds with fragments Re (CO) 3 (NN) and ligands oxime and oximato, as well as the systematic study of the reactivity of the past versus various electrófilos organic products has been characterized by methods spectroscopic and X-ray diffraction The fourth chapter is devoted to the study of reactivity face electrófilos organic complexes fosfuro [Re (PPh2) (CO) 3 (NN)]. The product of the reaction with carbon disulfide shows the creation of a computer link, keeping the link Re-P, in contrast to what is on the reactivity of the complex hidroxo. The most interesting results of this chapter are those obtained in the reactions with olefins and acetilenos activated, in which case it leads to the activation of the ligands 2.2 '-bipiridina or 1,10-fenantrolina, processes unprecedented in chemistry organometálica. In the case of the reaction with acetilendicarboxilato dimethyl (DMAD) there is a migration 1.3 Hydrogen, coupled with a change in position of a double bond in the product kinetic control, thereby obtaining a final product in which the double bond is combined with the system of two aromatic rings from fenantrolina initial. The final chapter includes an extension of the group's previous work with the complex [Re (N = Ph2) (CO) 3 (NN)]. Here we study the reaction of this unique complex with DMAD obtained in the sale of the same ligand bicíclico result of a coupling of the fragments N = CPh2, CO and DMAD. Moreover, this chapter is included in the synthesis, using a method different from that previously had yielded the complex [Re (N = CPh2) (CO) 3 (NN)], otherwise complex alquilidenamido derived imiduro generated from of benzonitrilo and acetiluro, and the full characterization of it.

Author: NIETO ALONSO SONIA.
Year: 2005.
University: OVIEDO.
Place of defense: DEPTO.DE QUIMICA ORGANICA E INORG.
Place of preparation: FACULTAD DE QUIMICA.

Summary: In this paper we develop and characterize new organometallic compounds which are present in some ligands ditópicos capable not only of coordinated to the metal, but also liaise with anions external hydrogen, and is studied both in solution and in the solid state, the interaction between these compounds and various anions. In most of these compounds, the compound that holds such ligands ditópicos is cationic, so that the electrostatic attraction between himself and the external anion joins the aforementioned hydrogen bond. In most of these cationic complexes, has been used as contraión the tetraarilborato BAr'4- (Ar '= 3,5-bis (trifluorometil) phenyl), in order to minimize its competition with anion external interaction with cationic receiver. In most of the compounds used as recipients, the metal fragment is fac-Re (CO) 3, chosen because it is cinéticamente inert, which allows the use of ligands ditópicos monodentados, without which they are displaced by the external anion (which it has been proved that it happens when you are using other metal fragments, such as fac-Mn (CO) 3 or fac-Mo (3-alilo) (CO) 2). Moreover, the geometry of this portion allows that, when used as ligands ditópicos three ligands monodentados, they are in a mutually fac provision, which allows their groups giving hydrogen bond could converge on a single external anion. The most extensive studies have been carried out with the type compounds fac [Re (CO) 3 (Hpz) 3] [BAr'4] (Hpz = pyrazole). For these, both structures in the solid state, as determined by X-ray diffraction, as studies carried out in solution, show that two, not three, the pirazoles that interact simultaneously with the external anion, which is attached to the distortion with respect to the geometry octaédrica that involve the simultaneous interaction of the three pirazoles. These studies were extended to compounds that two of the three ligands ditópicos are pirazoles, and the third is a aminopiridina. Within the compound with three ligands monodentados have been prepared and studied several in which these ligands are coordinated through a nitrogen atom, which joins a hydrogen, this being NH group which acts as liaison giver hydrogen. Among these compounds, which contains three ligands tetrametilguanidina proved to be stable against the displacement of the same by external anion. In other compounds studied in this work, ligands ditópicos are bidentados. Thus, through the coupling of acetonitrile and pirazoles in the presence of fragments carbonílicos of rhenium appropriate, are obtained ligands pirazolilamidino, which are coordinated to the metal through two nitrogen atoms. One of them is actually a group NH, capable of acting as a giver of hydrogen bond. In compounds of this type in which there is also a ligand pyrazole, NH his group and ligand pirazolilamidino are simultaneously hydrogen bond with an external anion found that receptors resulting cationic show a marked preference for the anion chloride. In this paper have also been used as ligands ditópicos bidentados the 4.4 'bis (carbamoyl) -2.2' -bipiridinas and 1,2-bencenodiamina, for which studies the influence of the nature of metallic fragment ( his state of oxidation and its cargo) on the behavior of the resulting complex as the recipient of anions. Both ligands bidentados have been used metal fragments octaédricos, in which to obtain cationic compounds, it has been necessary to block a coordination position through a ligand monodentado neutral 8 not lábi 378 l, whose possible decoupling could be detected in a simple and unmistakable, and non-hydrogen bond acceptor, which is elected terc-butilisocianuro.

Author: PEREZ GONZALO MARTA.
Year: 2005.
University: OVIEDO.
Place of defense: DEPTO DE QUIMICA ORGANICA E INORG.
Place of preparation: FACULTAD DE QUIMICA.

Summary: This dissertation focuses on the study of the reactivity of ligands difosfinocetenimina formula (PPh2) 2C = C = NR, both free and coordinated various metal centers. Thus, the reaction of olefins with free ligand electronically poor passes through a cicloadición [3 +2], where difosfinocetenimina serves as 1.3 dipole, to generate new fosfaheterociclos type 5-fosfol. For their part, difosfinoceteniminas N-arílicas involved in a multi-reaction with isocianuros and water or alcohols, forming derivatives 5-azafosfoleno. There have been also ligands monofosfinocetenimina, from difosfinoceteniminas corresponding through oxidation or elimination of one of the groups difenilfosfino, has been analyzed and its reactivity in cicloadiciones with unsaturated molecules and their ability coordinativa. It has also studied the ability coordinativa of difosfinoceteniminas faced with a variety of metal ions (Cu (I), Ag (I), Au (I), Pd (II), Ru (II), Mo (0)), that has enabled the synthesis of mono-and polymetallic complexes containing functional groups cetenimina peripherals. These functional groups react with different databases such as water, alcohols, amines, methyl lithium, which leads to the formation of difosfinas funcionalizadas type difosfinoamida, difosfinoiminoéster, difosfinoamidina and difosfinoenamina, some chiral, which can be released from the center with excellent cash yields.

Author: TOMA LUMINITA MARILENA.
Year: 2005.
University: VALENCIA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA.

Summary: The working thesis concerns the area of molecular magnetism. The main objective is the synthesis and characterization magneto-estructural new systems with magnetic properties novel based on the anion cyanide. Used Chemical Coordination as a tool for this job. It was part of cianocomplejos stable number six and coordination formula [MIII (L) (CN) x] (x + lm) - (M = trivalent metal ion, L = ligand blocking polidentado) as ligands respect to metal cations or fully hydrated partially blocked with the goal of designing materials whose magnetic topology, nuclearidad and magnetic properties can be controlled. The work includes the synthesis, characterization structural and magnetic properties of more than thirty polynuclear compounds to bridge cyanide. The lack of a theoretical model to analyze the magnetic data (due to the complex topology of systems) necessitates an analysis of the effectiveness of the interactions of exchange across the bridge cyanide by theoretical calculations based on the theory of functional density (DFT) and quantum Monte Carlo method. They deserve special mention the crucial role played by synthesis of new magnetic mononuclear precursors and behavior chains magnet showing some compounds heterobimetálicos. This behavior is one of the most attractive in the field of molecular magnetism.

Author: AXET MARTI M. ROSA.
Year: 2005.
University: ROVIRA I VIRGILI.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA. URV.

Summary: The thesis is based on the development and application of ligands difosfito derived from carbohydrates in the reactions catalyzed hydrogenation of hidroformilación and for rhodium. It also explores the synthesis of metal nanoparticles stabilized with different ligands derived from carbohydrates. Part of the argument has focused on the synthesis of new difosfitos derived from carbohydrates, D-glucitol and the D-glucosamina, and its implementation as catalysts chiral ligands in different reactions. In Chapter 2 discusses the synthesis and characterization of new ligands difosfitos. This new series of ligands modular structure is characterized by tetrahydrofuran with symmetry C2, where you can enter different substituents on the ring and the phosphorus atoms and change the configuration of esterocentros from positions two five ring tetrahydrofuran. It also discusses the respective compounds coordination rhodium. The ligands difosfitos have been used in the reaction of hidroformilación asymmetric styrene and other related catalyzed substrates for rhodium. The rhodium complexes have been used as catalysts in the reaction of asymmetric hydrogenation of a-acetamidoacrilato methyl. The systems Rh / difosfito have provided moderate activities and high regioselectividades in aldehyde 2-fenilpropanal. The enantioselectividades observed were moderate (up to 46% ee) and heavily influenced by the nature of ligand. Effects are observed enfrontados between the configuration of esterocentros two five ring tetrahydrofuran and the substituents in these positions, with the best results with groups bulky tert-butildifenilsilil. It has obtained up to 60% ee in hidroformilación of 4-metoxiestireno. The intermediate species in the reaction hidroformilación have been studied by NMR high pressure. In all cases there has been the formation of the complex. [RhH (CO) 2 (L)] (L: difosfito) where ligands coordinated position ecuatorial-ecuatorial. The complex [Rh (cod) (L)] BF4 (L: difosfito) have been used as catalysts in the hydrogenation reaction of a-acetamidoacrilato methyl, observandose low conversions and enantioselectividades. The reaction of hidroformilación of alibencenos and propenilbecenos has been studied using Rh / difosfito derived from carbohydrates. In reaction hidroformilación of trans-anetol were obtained high regioselectividades (up to 86%): While the reaction hidroformilación of estragole were obtained low regioselectividades. In ingún case was observed asymmetric induction. Recently, we have achieved excellent results in the application of nanoparticles as catalysts. So have synthesized new nanoparticles rhodium, ruthenium and palladium by the approximation organometálica, stabilized by ligands derived from carbohydrates. Obteniéndose nanoparticles well crystallized in diameter between 6 and 2 nm. The ruthenium nanoparticles synthesized from [Ru (C8H10) (C8H12)] in the presence of ligands difosfito had an average diameter of 2.5 nm. The rhodium nanoparticles were synthesized from [Rh (? 3-C3H5) 3] and [Rh (u-OMe) (COD)] 2 also in the presence of ligands derived from carbohydrates. The characteristics of ananopartículas synthesized dependent on the cash and forerunner of the stabilizer used. The palladium nanoparticles are used as catalysts for the reaction of alkylation alílica obtained excellent results. The nanoparticles rhodium are used as catalysts for the reaction of hidroformilación styrene, with low conversions.

Author: ANGURELL PURROY INMACULADA.
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA - UNIVERSIDAD DE BARCELONA.

Summary: The work is presented is part of the chemistry of metalodendrímeros. Interest in the study of the chemistry of these macromolecules has grown considerably in recent years because of their potential applications in fields such as the catalysis, electrochemistry, photochemistry or magnetism. In this work we have synthesized dendrímeros with skeleton carbosilano funcionalizados on the periphery with groups -PPh2. The ability of this group to coordinate a variety of transition metals has allowed obtaining metalodendrímeros of rhodium, iridium and withheld first and third generation. Moreover, tested the catalytic properties of these compounds in homogeneous catalysis processes. Specifically, the metalodendrímeros of rhodium catalysts proved to be active catalytic hydrogenation process of 1-hexeno while those of ruthenium were tested as catalysts in the process of transfer of hydrogen from 2-propanol to cyclohexanone and good results were obtained in terms of activity. There have also been synthesized dendrímeros funcionalizados on the periphery with two metal layers. The interest in obtaining such systems with different metals in the same dendritic structure lies in its possible application in catalysis processes cascade. The strategy used for obtaining such systems has been to modify the periphery of dendrímeros funcionalizados with a first layer of metal ruthenium (above) by the introduction of a ligand ditópico, such as 4-piridildenilfosfina. This ligand is able to coordinate the center metal ruthenium in a selective way through the nitrogen piridínico, so that the function -PPh2 remains on the periphery of dendrímero unchanged. The coordination of this group to a second piece cash has enabled obtaining dendrímeros funcionalizados on the periphery with two metal layers. This methodology has resulted in the acquisition of systems dendríticos of Rh-Fe, Ru-Rh, Ru-Ru, Ru-Au and Ru-Pd. Lastly, have been synthesized dendrones phosphorus, first and second generation, funcionalizados in perfieria groups amono upon him water solubility or with metal fragments of ruthenium, which can be used for obtaining systems bis-dendríticos fit biphasic for catalysis.

Author: GONZÁLEZ ARELLANO MARÍA DEL CAMINO.
Year: 2005.
University: AUTÓNOMA DE MADRID.
Place of defense: INSTITUTO DE CIENCIAS DE MATERIALES DE MADRI.
Place of preparation: INSTITUTO DE QUÍMICA ORGÁNICA GENERAL.

Summary: In this Doctoral Thesis has developed a methodology for the preparation of metal complexes useful as homogeneous catalysts and another for heterogeneización by covalent bond with various inorganic carriers. The catalytic activity of these materials have been studied in various processes of hydrogenation and training liaison CC (Heck, Suzuki and homoacoplamiento). SUMMARY OF LIGANDOS AND COMPLEX HOMOGÉNEOS And HETEROGENEIZADOS It has prepared a series of ligands Schiff bases: (E) -6-terc-butil-4-metil-2- ([(2'S) -N-bencilpirrolidinil] metiliminometil) phenol, ( E) -6-terc-butil-4-metil-2- ([2'S) -N- (1-metilnaftil) pirrolidini] metiliminometil) phenol, (E) -6-terc-butil -4-metil-2- ( [(2 'S) -N- (2-metil naftil) pirrolidinil] metiliminometil) phenol, (R) -2-amino-2' - (5-metil-3-terc-butil-2-hidroxiben zilidenamino) -1.1 '- binaftilo and Bis (R) -2.2' - (5-metil-3-terc-butil-2-hidroxibenzilidenamino) -1.1 '-binaftilo in several stages, with quantitative yields and are almost as isolated compounds optically pure. The ligands act as tridentados, react with the acetates of palladium (II) and nickel (II) with acid tetracloroaúrico trihydrate giving rise to complex plano-cuadrados where eligando is coordinated to the metal through the phenol groups, imínico and amine ([N, N, O]) with displacement of one group or acetate chloride. Another goal was to develop a methodology for síntetizar the ligands heterogeneizados, to carry out this summary is part of percusor N-[(3-terc-butil-5-formil-4-hidroxifenil) methyl] - N '- (3 - trietoxisililpropil) containing urea in its structure a group trietoxisilano which allows heterogeneización of ligands on inorganic media (MCM-41, ITQ-2, ITQ-6 and síklice), formation of covalent bond (Si-O-Si) the silanoles the surface of the medium and its corresponding complexes palladium, nickel and gold, under the same conditions as for the synthesis of soluble complexes. STUDY OF ACTIVITY CATALÍTICA HIDROGENACIÓN complexes of palladium (II), nickel (II) and gold (III) has proven to be excellent catalysts in hydrogenation reactions of alquenos and iminas, under very mild with very high conversions in relatively short times . The metal complex heterogeneizados show greater reactivity than relevant homogeneous also can be reused in successive cycles without significant loss of catalytic activity. FORMATION OF LIAISON DC The complex palladium (II) show a high activity and Suzuki Heck reactions. The catalysts supported on ITQ2 are the most active in these reactions, their uniform and the other heterogeneizados, also can be reused up to eight times without significant loss of activity. In the case of complex gold (III) under the reaction conditions Suzuki obtained proceeds from homoacoplamiento arilborónico-arilborónico with quantitative yields. In all processes that have been developed are related to sustainable chemistry, reducing pollutants by improving the efficiency of reagents and solvents and developing environmentally acceptable routes to get organic produce important.

Author: MARTÍN PUIG PATRICIA.
Year: 2005.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: The report submitted contains significant input on the mixed oxide systems formed by Li and couples Transition metal (Cr-Ti, Mn-Ti and Cr-Mn) with spinel structure. These systems and others related to the subject of extensive research in the international context and the major contributions of this work include structural analysis, the study of magnetic and electrical properties, and especially the electrochemical characterization of the original materials synthesized. Among the most significant findings is the potential usefulness of some of these derivatives as electrodes in solid state batteries.

Author: PERLES HERNÁEZ JOSEFINA.
Year: 2005.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: This paper describes the design, synthesis, resolution crystal structure and characterization through various techniques type polymer organo-inorgánico formed from scandium, yttrium, lanthanum, terbio and ytterbium and ligands succinate, tereflalato and 1.5 - and 2,6-naftalendisulfonato. It describes the process of optimizing its synthesis and describes their aplciaciones in various catalytic reactions (Acetalización of aldheídos, oxidation of sulphides and epoxidación of linalool). In more concrete terms, describes the synthesis and characterization of succinatos of scandium [SC2 (C4H4O4) 2.5 (OH)] No, yttrium [Y2 (C4H4O4) 3 (H20) 2] n. NH2O and lanthanum [La2 (C4H4O4) 3 (H2O2] n. nH2O; tereflatlatos of scandium [Sc2 (C8H4O3] No, yttrium [Y2 (C4H4O4) 3 (H2O4)] No, lanthanum [La2 (C4H4O4) 3 (H2O) 4] ny erbio [Er2 (C4H4O4) 3 (H2O) 4] n; terflalato-sulfatos yttrium [Y6 (C4H4O4) 8 (SO4) (H2O) 8] No, erbio [Er6 (C4H4O4) 8 (SO4) ( H2O) 8] ne ytterbium [Yb6 (C4H4O4) 8 (SO4) (H2O) 8] No, tereftalato-sulfato ytterbium [Y4 (C4H4O4) 5 ((SO4 (H2O) 8] No, 1,5-naftalendisulfonatos scandium of [Sc2 (C10H6s2O6) (oh4] NE ITRIO [and (C10H6S2O6) (OH) (H2O)] ny the 2,6-naftalendisulfonatos of scandium [Sc2 (C10H6S2O6) (OH) 4] ne yttrium [Y4 (OH) 10 (H2O) 4] n (C10H6S2O6) n. It also describes the use of new materials in the above-mentioned reactions of catalysis, establishing relations between the composition and structure of materials and their catalytic activity. Likewise, it reveals the effectiveness in adsorption of H2 and N2's tereflalato of scandium.