COORDINATED COMPOUNDS

Author: DÍEZ GÓMEZ VIRGINIA.
Year: 2003.
University: BURGOS.
Place of defense: CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: In this paper we study the synthesis of complexes of palladium (II) and platinum (II) with ligands nitrógenodadores of rates: 2 - (arilaminometil) pyridine, 2 - (arilmetilaminometil) pyridine, 2 - (arilaminometil) thiophene and 8-( arilamino) quinoline. In all cases is obtained complex with a ligand coordinated by two nitrogen atoms except in the case of ligand 2 - (arukanubinetuk) thiophene. The complex which is obtained with two ligands coordinated solely by the nitrogen atom. It also explores the estereoquímica such complex analyzing the possibilities of isomería cis / trans, configuracionales R / S alos around atoms of nitrogen amínicos and conformational in rings qulato trained. Some interpretations apply geometric calculations mecanocuánticos DFT. It proceeded to desprotonación of amine complexes were studied and the different developments experienced by families of compounds. Major developments ebservadas are training bridges amide in palladium complexes with ligands auxiliary easily desplazables and nitrogen ligands giving unhindered aesthetic and oxidation to give rise to complex imina when hydrogen atoms in position B is impeded the formation of bridges and there is an oxidizer in the middle. That oxodante can be oígeno atmospheric. We only get stabilize the complex terminal amide twice-platinum complexes where dimerización is cinéticamente unfavorable and ligands with hydrogen atoms in position B, but in terms of absence regurosa of oxidantes.En these conditions ensures that these complex show reactivity characteristics of the complex amide. - When using a ligand without atoms hifrógeno in position B and that it is possible to stabilize the load group aromatic amide groups to adjacent. It has studied the oxidation of thermally activated amine complexes dissolved in dimetelsufóxido (refer to such solutions to global warming). Discusses the influence of the metal center and the substituents in the ligand nitrogen in the process of oxidation. It also discusses the possible mechanisms for the oxidation of amine complexes, proposing a path different reaction to the most widely accepted composite of other metals of the platinum group.

Author: SARABIA BELLO CRISTOBAL.
Year: 2003.
University: ALMERÍA.
Place of defense: CIENCIAS EXPERIMENTALES.
Place of preparation: FACUALTAD DE CIENCIAS EXPERIMENTALES.

Summary: The main aim of the thesis is the synthesis, acractirización and study the reactivity of derivatives alteniclidenicos of ligano NPP and metals of the first series of transition in a position not inert, in order to obtain compounds with catalytic properties that are económicas.ç have been sintering and characterized complexes NPP with ZnUa, CdAa and AgNO3, Coa2, and Cu (A04) 2, estudiandosa lareactividad the same versus reactive nucleofilos CO, H2S, NH3 and alquinos terminals. It was not possible to obtain derivatives alenilidénicos, although composite structures with surprising and interesting reactivity.

Author: MASPOCH COMAMALA DANIEL.
Year: 2004.
University: AUTÓNOMA DE BARCELONA.
Place of defense: FACULTAT DE CIENCIAS QUÍMICAS.
Place of preparation: ESCUELA DE DOCTORADO Y DE FORMACIÓN CONTINUADA.

Summary: The molecular porous materials have become in recent years in some serious candidates to be used as substitutes of zeolites. Here, in this Doctoral Thesis, has designed a new strategy for obtaining synthetic materials or organic molecular metal hybrids that combine features purely organic porous, with large pores, and magnetic properties interesting. With this new generation of materials seeks access to new applications, such as the manufacture of new magnetic sensors selective. Until this time, the design of materials of this kind was a challenge, because certain contradictions appeared synthetic. Our approach is based on the use of organic radicals stable as constituents of these materials. An initial molecular nanoporoso and materials with magnetic ordering (named MOROF-1, Metal-Organic Radical Open-Framework) has been synthesized using a metal ion such as copper (II) and a radical policlorotrifenilmetílico trifuncionalizado three carboxylic groups (D. Maspoch et al. Nature Mat., 2002, 2, 190). This compound presents characteristics nanoporososas really extraordinary. The size of its channels is about 3 nm. In addition, evacuation and absorption of solvent molecules (methanol or ethanol) causing some structural changes surprising: the material is behaving like a molecular sponge, giving excellent conditions to be able to act as a sensor of solvents such as methanol or ethanol. This highly porous structure is ordered ferromagnéticamente at low temperatures. Moreover, within the Doctoral Thesis, you can find other materials with magnetic properties porous and interesting. Moreover, the use of these radicals as blocks linked by bridges paramagnetic molecular hydrogen has also enabled the acquisition of the first purely organic molecular materials and magnetic porous, which are stable in absencia solvent and have a high thermal stability (275Â ° C ). Thus, the packaging of radical PTMDC (Dicarboxílico 9 forms a molecular paramagnetic materials (POROF-1) with a composite structure of nanocontenedores molecular hydrophobic up 1nm. Moreover, the radical PTMTC (Tricarboxílico) generates a second purely organic porous materials ( POROF-2), which is ordered ferromganéticamente.

Author: GONZÁLEZ PRIETO RODRIGO.
Year: 2004.
University: COMPLUTENSE DE MADRID.
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS.
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS.

Summary: This paper describes the synthesis and characterization of a series of compounds dinucleares of ruthenium (II, III) with elace multiple metal-metal.En First deals with the study of monohaleotetracarboxilatos, Ru (u-O2CR) 4X (X = CI , Br, I) whose order in the solid state is determined mainly by the carboxylate ligand, but also influence the axial ligand and the solvent in which cristalizan.Se also describes a general procedure for the synthesis of anionic complexes of dirrutenio (II, III), Q [RU2X2 (U-O2CR) 4] (X = CI, Br, I, Q = NET4 +, PPH4 +), whose structure in the solid state shows that the contraión also has influence over the management of units dimetálicas.Estas species solvatocromismo, which is related to polarizabilidad of ligand halide. It has been achieved by replacing the axial halide groups perrenato (REO4), resulting in linear polymer compounds or zigzag, aunqu3e is also possible formation of anionic complexes or with a provision cation / anión.Utilizando groups cyanate (NCB) or dicianatoargentato [g (ocn) 2-], obtained in the form of compounds in zigzag chains, in which groups cyanate act as a bridge between two metal atoms through the oxygen. The complex cationic tetracarboxilato of dirrutenio (II, III) are reduced with hydroquinone, in the presence of a base resulting in the corresponding complexes dirrutenio (II). Moreover, it has succeeded in preparing derivatives tetrakis (triacenuro) dirrutenio (II III) and dirrutenio (III) stable. Finally, to compound RU2BR (U-O2CCH2CH3) 4, have been performed calculations using the theory of functional density (DFT) and have conducted studies using atomic force microscopy (AFM). The results suggest that it may behave as a molecular wire conductor.

Author: FIGUEROLA SILVESTRE ALBERT.
Year: 2004.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: DEPARTAMENTO DE QUÍMICA INORGÁNICA.

Summary: In the work described in this report have been prepared and structurally characterized studied from a viewpoint different magnetic systems based molecular ions with mixed block fyd used in all cases Ln (NO3) 3.xH2O where Ln3 + = any ion lantánido state oxidation +3, and K3 [M (CN) 6], where M3 + = Fe, Co, Cr, as reagents heading mixed aqueous solution. The addition, in each case, various binders blockers such as NN '-dimetilformamida or 2.2' -bipiridina, and the very nature of ions Ln3 + and M3 +, has resulted in systems of different nuclearidad and / or dimensionality always ligand bridge cyanide. Because there is no single model that includes the effect of coupling espín-órbita, the effect of crystalline field of ion exchange and magnetic described by tensor Anisotropic J, the study of magnetic interactions between each of the ions Ln3 + and ion Fe3 + in this whole set of compounds has been carried out through the application of a qualitative approach that allows decipher the nature of this interaction but not its magnitude. So we have been able to study the evolution of the magnetic interaction along the whole family ion lantánidos (III). The presence of crystalline environments low symmetry ions Ln3 + leads to a magnetic anisotropy in these compounds readily observable at low temperature, where the values of XM do not follow the law of Curie. The magnetic anisotropy of the simpler systems (compounds dinucleares LaFe, CeCo and CeFe) was studied using measures of monocristal and magnetic resonance paramagnética electronic monocristal (rpe). The magnitudes and directions of the three components of the tenors g for ions Ce3 + and Fe3 + were determined independently by the spectra of rpe of monocristal of compounds dinucleares CeCo and LaFe respectively. The use of Gd3 + as ion Ln3 + and [Cr (CN) 3] 3-instead of [Fe (CN) 6] 3-in the synthesis of new compounds mixed 3d-4f has greatly simplified the magnetic survey of this type of systems since the ion Gd3 + no coupling espín-órbita, unlike the rest of ions Ln3 + pramagnéticos, and the ion Cr3 + is especially isotropic. That allowed adjust the magnetic data of these compounds using Hamiltoniano spin isotropic obtaining values of constant exchange isotropic magnetic equal to or less than 1 cm-1, predictable values taking into account the characteristics of the systems 3d-4f. Finally, the attempt to synthesize compounds mixed df high nuclearidad has resulted in a system with type structure with a cluster ion Ce4 + diamagnético centerpiece, with a key role as a template ion, surrounded by eight ions Mn3 + coupled ferrmagnéticamente between them. It also won two systems triangular Cr3 + showing the presence or absence of spin frustration depending on the symmetry of the molecule.

Author: GAY MARÍN MARINA.
Year: 2004.
University: BARCELONA.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: UNIVERSITAT DE BARCELONA.

Summary: * It has synthesized a family of diaminas tertiary through various methods, in a few steps and with acceptable yields. * The timing of these diaminas tertiary to platinum (II) is not something that happens as expected, due to the impediment estérico of the methyl groups. But they got two organometallic complexes of platinum, where ligands are coordinated through a double bond. * From then switched strategy and synthesized diaminas primary bicíclicas and monocíclicas, to facilitate coordination to platinum. We used different methods of synthesis versatile, so azide route via nitrilos, based on Diels - Alder reaction from commercially available products. There was a family of ligands with a skeleton-type 1,2-bis (aminomethyl) cyclohexane, with different structural characteristics, with the intention to study its influence on the activity. * Coordination of diaminas primary obtained from the platinum proceeded as expected and extracted complexes platinum (II) corresponding amines coordinated through amino groups to form a ring of seven stages. It worked with chlorides and iodides as ligands labile. The replacement thereof by oxalate or other ligands capable of modifying the pharmacokinetics of the compound will be studied in the future. * The DNA is the main target of such biological compounds. We studied the qualitative interaction of platinum with DNA obtained through different techniques. With the circular dichroism have studied changes in its secondary structure. The changes in the tertiary structure of DNA revealed by agarose gel electrophoresis. Finally, we saw the images of the technique of atomic force microscopy. It was generally observed that all complexes, to a greater or lesser extent, are able to modify the structure of DNA and correlations have been established on the basis of the structural features of the ligands of non-labile complexes. * We also test antiproliferative activity with complexes synthesized platinum (II). One of the two organometallic complexes, but not a classical structure, was active against various pairs of cell lines sensitive and resistant to cisplatin. With the rest of complexes were conducted in vitro cytotoxicity studies with cell lines A2780 and A2780cisR, sensitive and resistant to cisplatin, respectively. These studies have established, in a first approximation, correlations structure within this family of complex. In general all the complex have been active and in some cases concentrations below cisplatin. Furthermore, all factors presented below cisplatin resistance.

Author: MUGA RELLOSO IÑAKI.
Year: 2004.
University: PAÍS VASCO.
Place of defense: FACULTAD DE CIENCIA Y TECNOLOGIA.
Place of preparation: FACULTAD DE CIENCIA Y TECNOLOGIA.

Summary: The design and synthesis of new compounds coordination with magnetic properties of interest is an area of great interest in the field of inorganic chemistry. Special relevance have acquired compounds coordination high dimensionality, the result of the reaction of transition metal ligands type pseudohaluro, cyanide and oxalate in certain proportions. The work presented in this report consists of the study of polynuclear complexes with ligands oxalate, pseudohaluro and cianocomplejos, mechanisms of interaction and structural correlations magnet. Our study will focus on the complex obtained from the reactions between complex precursor [Ni (dien) (H2O) 2 (ox)] (PF6) 2 2H2O and different types of ligands. Of great interest, both from the structural point of view as magnetic, are complex where the oxalate ligand is coordinated over a metal species to form polynuclear.

Author: REINOSO CRESPO SANTIAGO.
Year: 2004.
University: PAÍS VASCO.
Place of defense: FACULTAD DE CIENCIA Y TECNOLOGIA.
Place of preparation: FACULTAD DE CIENCIA Y TECNOLOGIA.

Summary: This paper presents the study synthetic, structural and magnetic properties of the hybrid materials inorgánico-metalorgánico based polioxometalatos type Keggin and dimers cationic copper (II) -carboxilato bridge blocks as inorganic and metalorgánicos respectively. The objectives have been to optimize the synthesis method using self-assembly of blocks on a non-hydrothermal and investigate the influence of the reaction medium in composition, dimensionality and connectivity between blocks of material hybrid end. It has been used polianión [SiW11O39Cu (H2O)] 6-as a bloc inorganic; dimers [(Cu (fen) (H2O)) 2 (c) 2] 2 +, [(Cu (fen) (H2O) 2) 2 (ox)] 2 + and [Cu ((bpy) (H2O) 2) 2 (ox)] 2 + as blocks metalorgánicos and tampons Hac / Mac as a means of reaction (M = Rb, NH4, K and Na; fen: 1 , 10-fenantrolina; bpy: 2.2 '-bipiridina; ac: acetate; ox: oxalate). As a result, there are ten different compounds from inorganic combination of a block with one of the three metalorgánicos one of the four media reaction. In addition, there are two compounds with polianión [SiW12O40] 4-and the complex [Cu (bpy) 2] 2 + and [Cu ((bpy) (H2O) 2) 2 (ox)] 2 + as blocks metalorgánicos With the dímero acetate bridge have prepared four compounds, two type ion and two cotienen polianiones hybrid discrete. On the other hand, with the oxalate dímero bridge and fenantrolina as ligand peripherals have only been able to obtain two new examples of polianiones hybrid discrete. Finally, in dímero oxalate bridge and bipiridina as peripheral ligand have been obtained four other compounds, one containing a polianión hybrid discrete and 3 examples of materials extended monodimensional character. The two compounds with polianiones [SiW12O40] 4 - are examples of hybrid materials of two-dimensional character. The compounds obtained have been characterized by elemental analysis, atomic absorption and ICP, spectroscopy FT-IR and thermogravimetry. The structural study has been carried out by X-ray diffraction on monocristal or shows policristalina while to study their magnetic properties have been used to mediads of spectroscopy and magnetic susceptibility REP.

Author: González Lorenzo Marina.
Year: 2004.
University: A CORUÑA.
Place of defense: Facultad de Ciencias.
Place of preparation: Facultad de Ciencias.

Summary: This Doctoral Thesis has been raised with the aim of deepening the theme of selective complexation of ions Ln (III). It has evaluated the potential complexing of the recipients macrocíclicos type ether lariat: N, N '- bis (2-salicilaldiminobencil) - 4.13-diaza - 18-corona-6 (H2L1), N, N' - bis (2 - salicialaldiminobencil) - 1.10-diaza-15-crown-5 (H2L2), N, N '- bis - (2-saliciladiminobencil) - 4.10-diaza-12-crown-4 (2L3), N-2 - salicialaldiminobencil-1-aza-18-crown-6 (HL4). As dianiónica, the new ether lariat bibraquial base Schiff H2L2, derived from 1.10-diaza-crown-5, is able to form stable complexes with more ions Ln (III) their analog H2l1 derived from the 4.13 - diaza-18-crown-6. It has been found that H2L2 form stable complexes with ions Ln (III), Ln = La-Ho. The structures in the solid state indicate that the cation complex [Ln (l2)] ion Ln (III) was perfectly encapsulated inside the cavity macrocyclic generated receiver. The properties fotofísicas reveal data importanes: emission spectra at high resolution of complex Eu (III) show the presence of different environments around the coordination ion lantánido that are attributed to different conformations of the macrocyclic cavity. The low energy state triplete receptor macrocíclico can also transform visible radiation absorbed by the ligand in near infrared radiation emitted by the Nd (III) in the corresponding complex. This property suggests the possible application of these complexes in the transformation of visible radiation emitted radiation in the near infrared. As desprotonada, ether lariat bibraquial N, N '- bis - (2-salicilaldiminobencil) - 4.10-diaza-12-crown-4 (H2L3) form stable complexes with ions smallest of the series of lantánidos (Ln = Ho-Lu). Unable to aisalar complexes lantánidos with members lighter in the series, which suggests a degree of selectivity toward ions lantánidos heavier. The X-ray structures of monocristal the complex Ho (III) and Er (III) show that the metal ion is directly linked to the eight atoms of giving ligand macrocíclico. It has been found as complexes erbio and yterbio to observe the emission characteristics of these ions in the near infrared in acetonitrile as methanol. The complex [Er (L3)] is a unique example because it allows to observe the emission of Er (III) in the middle prótico. Ether lariat monobraquial N-2-salicilaldiminobencil-1-aza-18-crown-6 (HL4), as desprotonada, is able to form stable complexes with ions of the first half of the series of lantánidos (Ln = La-Tb). This receiver was xomporta as a less selective ion towards lighter ions in the series of lantánidos compared with the receiver H2L1, èsar of qie eñ ta, the crowning ap deñ fragment is similar in both receptore. This is attributed to the lower stiffness receptor HL4 regarding H2L1 due to the presence of a single chain hanging in the first. The selectivity observed has been streamlined through theoretical calculations made in vacuum at Hartree - Fock (HF).

Author: SENS LLORCA CRISTINA.
Year: 2004.
University: GIRONA.
Place of defense: UNIVERSIDAD DE GIRONA.
Place of preparation: UNIVERSIDAD DE GIRONA.

Summary: We have synthesized two new complexes mononuclear Ru, made [RuCl2 (Hbpp) (dmso) 2], from the reaction between [RuCl2 (dmso) 4] and Hbpp. The fact that only three of the six possible stereoisomers are obtained from this reaction has been rationalized on the basis of structural factors and electronics. These complexes have been characterized so structural espectroscópica and electrochemistry. In acetonitrile amid core, the trans isomer, cis- [RuCl2 (Hbpp) (dmso) 2] resulting in processes isomerization liaison of a ligand dmso when the Ru (II) is oxidized to Ru (III). The thermodynamic and kinetic constants for the process have been determined by voltametria cyclical. The irradiation, trans cis- [RuCl2 (Hbpp) (dmso) 2] and cis (out), cis- [RuCl2 (Hbpp) (dmso) 2] with UV light or solar leads to reactions fotosustitución a ligand dmso for a molecule of acetonitrile. The new complex has been characterized in solution by electrochemical and spectroscopic techniques. Both complexes are useful catalysts in the transfer of hydrogen isopropanol to acetophenone, obtaining 1-feniletanol as a single product and a 42.1% conversion (36.1 cycles metallic) 80Â ° C with the trans isomer, cis- [RuCl2 (Hbpp) (dmso) 2], which is significantly more effective than complex cis (out), cis- [RuCl2 (Hbpp) (dmso) 2]. The reaction of cis (out), cis- [RuCl2 (Hbpp) (dmso) 2] with trpy leads to the two geometric isomers of the complex [Ru (Hbpp) (trpy) (Cl)] +, the in and out . These complexes have been isolated and characterized by structural techniques, spectroscopic and electrochemical. These complexes chlorine has been used as precursors for the synthesis of complexes with similar aqua ligands (in, out- [Ru (Hbpp) (trpy) (H2O)] 2 +) and pyridine (in, out- [Ru (Hbpp) (trpy) (py)] 2 +), which also have been isolated and characterized. The acid properties of the aqua complex, and complex out-py have been studied in detail by voltametria cyclical and through assessments espectrofotométricas acid. The mathematical treatment of the data thus obtained has allowed us to determine the values of pKa for different balances of protonación the complex in the states of oxidation II and III. The complex out-aqua has proven to be a good catalyst for the electrochemical oxidation of alcohol benzílico, presumably benzaldehido. The rate constant of the second order for the process has been determined as 17.1 M-1 s-1, by mathematical simulation. The dímero with a jumper chlorine, [Ru2Cl (bpp) (trpy) 2] 2 + has been prepared by two different synthetic routes. The dímero with a jumper acetate was obtained by reaction of chlorine dímero with excess sodium acetate. The dímero two aqua ligands [Ru2 (bpp) (trpy) 2 (OH2) 2] 3 + can be obtained by acid hydrolysis of acetate complex with a bridge or by hydrolysis core complex with a bridge chlorine. These complexes have been characterized by structural techniques, spectroscopic and electrochemical. The solutions of dímero two aqua ligands are unstable in acid medium to coordinating anion of the solution over time. The acid properties of dímero with two coordinated water have been studied by voltametria cyclical and through electrolysis experiments to potential controlled. The pKa for desprotonación one of the aqua ligands has been determined through an appraisal spectrophotometric acid as 6.7. This value so low pKa is attributed to the formation of the entity (Ru2O2H3), thermodynamically favorable. The spectra UV-vis for different states of oxidation aqua dímero, RuIIRuII to RuIIIRuIV, have been obtained by chemical and electrochemical oxidation of the complex. Have been carried out kinetic studies of the oxidation step at a time, RuII, II RuIV, IV, and have determined the constants of oxidation segund 8 or order 88c for the various processes of oxidation. The ability of dímero water in the oxidation of water to molecular oxygen has been investigated in homogeneous solution using CeIV as an oxidant. The evolution of oxygen has been shown by gas chromatography. It has achieved an efficiency of 73% and 18.6 cycles catalytic when 1.83 x 10-6 mol of dímero have been mixed with an excess of 100 equivalent of cerium. The dímero with two waters also catalyzes the oxidation of water in a heterogeneous, with the complex adsorbed on a membrane nafion, but the efficiency is lower. It has been proposed a mechanism intramolecular for the oxidation reaction of water. It consists of a 4 electron oxidation of dímero, RuII, II RuIV, IV, which reacts with water to form oxygen and reverts back to the state of oxidation II,. This model is consistent with studies of the evolution of catalytic oxygen depending on the concentrations of cerium and catalyst, conducted in acidic solution uniform, showing that oxidation to 4 electrons water is catalysed by a single molecule complex under high concentrations of cerium. The constant pseudo-primer-orden for the evolution of oxygen has a value of 1.4 x 10-2 s-1, which is one of the highest values of constant obtained so far. Unfortunately, the aqua dímero deactivated during the catalysis process leading to a sort orange, which we are currently trying to characterize.

Author: AGUADO SEVILLA JAVIER ESTEBAN.
Year: 2004.
University: ZARAGOZA.
Place of defense: UNIVERSIDAD DE ZARAGOZA.
Place of preparation: UNIVERSIDAD DE ZARAGOZA.

Summary: The work focuses on the synthesis and reactivity of derivatives ferroceno that can act as ligands face various metal centers. It is derived from simple ferroceno to synthesize complex molecules that offer giving oxygen atoms, nitrogen, phosphorus and sulfur. The first part focuses on the preparation of intricate gold and silver with ferrocencarboxilatos and has been coordinating four gold atoms in the compound [Au4 (Fc (COO) 2) (PPh3) 4] (ClO4) 2 (Fc = (h5-C5H4) 2Fe). The second part is devoted to the synthesis of various ligands amidoferroceno 1.1 'bis [(6-metil) -2-piridil) amide] ferroceno, 1.1' bis [N N-bis (2-piridil) amide] ferroceno and 1.1 'bis [N N'- (2 - (difenilfosfino) ethyl) amide] ferroceno and the corresponding complex of gold, silver and copper. Derivatives have been prepared mono, di and tetranucleares. Highlighting the formation of several one-dimensional polymer silver with ligands triflato bridge, as in [Ag2 (OTf) 2 (Fc (Npy2)], and obtaining dimero [Au2 (Fc (CONCH2CH2PPh2) 2)], which presents an interaction aurofilica short and gold atoms attached to the phosphine group and the nitrogen amiduro. reaction of a (clorocarbonil) ferroceno with cysteamine gives rise to two derivatives, the first is a compound cycling [Fe (h5-C5H4CONHCH2CH2SCO (h5-C5H4)] and the second Fc (CONHCH2CH2SH) 2, which is easily oxidized to disulfide cyclical [Fe (h5-C5H4CONHCH2CH2SSCH2CH2CO (h5-C5H4)]. were also studied asymmetric ligands such as Fe (C5H4PPh2) (C5H4SPh) and Fe (C5H4PPh2) (C5H4 ), which are coordinated group metals 11 through atoms P SyP, C. The last part of the work is devoted to the reactivity of oligopiridinas containing unity ferroceno. thus have been prepared with the new complex ligands a ( bipiridil) ferroceno, ferrocenilterpiridina and a (ferrocenil) quinquepiridina. Notably synthesis [Au3 (C6F5) 3 (Fcterpy)], which is the first compound with a ligand type terpiridina linked to three different metals, and also the preparation of complex helical silver [Ag2 (Fcquinquepy) 2] (OTf) 2. addition, it has achieved a novel synthetic route for obtaining indolicinas from 2 - (3-ferrocenil-1-oxoprop-2enil) pyridine by reaction with silver complex as [Ag (OTf) (PR3)].

Author: GÓMEZ SEGURA JORDI.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: ICMAB-CSIC.
Place of preparation: ESCUELA DE POSTGRADO UAB.

Summary: The magnets unimoleculares correspond to the high-spin complex metal marked with magnetic anisotropy. Therefore, there is an energy barrier for the interconversion of the magnetic moment of spins in the opposite direction, causing slow speeds relaxation of the magnetization. So, there are interesting magnetic properties such as magnetic susceptibility curves out of phase or hysteresis curves. Characteristics of the magnetic domains. Additionally, as is attributed to its size, mesoslópico, observed phenomena rejación of magnetization by quantum tunneling effect. For the generation of future quantum computers at the molecular level, based on magnets unimoleculares, it is necessary to develop a variety of new methods that allow deposit on the surface in a controlled manner, whether molecular aggregates or single molecules to be used as magnetic information BITS .

Author: Villarreal Tolchinsky Laura.
Year: 2005.
University: AUTÓNOMA DE BARCELONA.
Place of defense: Facultad de Ciéncias.
Place of preparation: Autónoma de Barcelona.

Author: PEREIRAS GABIÁN GUMERSINDO.
Year: 2005.
University: VIGO.
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The biological activity of tiosemicarbazonas (= TSCs), tumor, antiviricas, antifungal and antibacterial and its complex has been the home study coordination chemistry of these ligands. These compounds are multifaceted ligands which can be coordinated so as neutral as is his style desprotonada. Numerous metal complexes have been studied chemically and by x-ray diffraction. So surprisingly, are less known and rhenium complexes tecnecio with tiosemicarbazonas. In the present work, the study of the behavior of coordinating some of these ligands containing rhenium (I) and tecnecio (I). The reaction of three ligands tiosemicarbazona from formilferrocenoaldehído (group H, Me or Ph linked to nitrogen tioamídico) with the precursor [ReX (P) s] (X = CI, Br) results in six adducts of general formula [ReX (P) J (HL)]. Data espectrocópicos and X-ray diffraction study of monocristal confirm the formation of a five-member ring chelate by coordinating atom of sulfur and nitrogen hidrazínico (N3). The halogen ligand the labilizado by desprotonación complex [ReX (CO) 3 (HL)] complexes formed dimers [Re2L2 (CO) 6] in which atoms of sulfur establishing bridges between the two rhenium atoms. The reaction of three ligands TSCs derived from 4-acetilpiridina gives results as six adducts with the formula similar to those derived from fonnilferrocenoaldehído but by studying X-ray showed that the compounds consist of dimers of general formula [Re2X2 (P) or ( HL) 2] 'The ligands TSC cuentean the two atoms through rhenium atoms of sulfur and nitrogen from the pyridine. In addition, the solvent used in the crystallization can modulate the packaging of dímero molecules. However, the products obtained by reaction of the TSCs derived from the 2.2 '-dipiri1cetona differ sharply with previous compounds since analytical data show a composition corresponding to the formula [Re2X (L) (CO) 6]' In this case, the ligand suffer desprotonación and chain tiosemicarbazida bypassing between the two rhenium atoms, one of them has lost halogen ligand. The last metal atom is coordinated by the TSC through the atoms of sulfur and nitrogen azometínico ypiridínico forming two rings chelate five members, while it forms a ring chelate by coordiIjación the six members of rhenium atoms through the nitrogen hidrazínico and piridínico another pyridine ring. The reaction of the adducts [ReX (COMCH3CN) 2] (X = CI, Br) with TSC ligands derived from p-cetoéstres and pcetoamidas, at room temperature and using chloroform as a solvent, obtained adducts whose structure is similar to those found in derivatives formilferrocenoaldehído, while the reaction to reflux in toluene results in this kind of adducts and products resulting from the ciclación of ligands TSCs and training derivatives Pyrazolone. Studies process cielación by RMN-1H of adducts yel isolation of the adducts Pyrazolone suggest that the process of cielación was initiated in the field of coordination of rhenium the reaction rate is determined by impediments estérico (size and halogen groups rents in the ester groups). The reaction is probably initiated by the desprotonación delligándo TSC, losing the group -RO. And ciclación as adduct pírazolona that desprotonación and release of halogen atom gives complexes pirazolonato formula [Re (pyz) (CO) 3] 'But you can only get solid pure estequiometría [Re (pyz ) (CO) 3] in toluene reflux for 20 hours with the ligand and [ReCI (P) s]. The compounds were isolated as crystals by X-ray diffraction studies showed its nature p 8 olinuele 511 ar. The Pyrazolone ligands are coordinated through the rhenium atoms of sulfur and N (3) Yal oxygen of a neighboring molecule. The formation of structures tetrámero or trímero depends on the substituyente on nitrogen tioamídico. Studies with the cation Tc (I) were focused on the reactivity of derivatives TSCs of 4-aceti] pyridine and 2.2 '-dipiridi1ctona. The X-ray diffraction studies show that the first individual compound is similar to those arising from rhenium. However, coordination with the second ligand atom tecnecio only becomes exclusively by the nitrogen atoms of pyridine.

Author: Pardo Marín Emilio.
Year: 2005.
University: VALENCIA.
Place of defense: Facultad de Química.
Place of preparation: Universidad de Valencia, Facultad de Química.

Summary: The objective of this thesis is the development of new metal complex polynuclear coupled magnetically which is one of the greatest challenges in magnetism supramolecular .. The Coordination Chemistry provides an adequate tool to meet our goals. The contents of the thesis has been distributed into four separate chapters in response to various factors below relate. En el capítulo I se presenta un método racional para la síntesis de oxamatocomplejos dinucleares de cobre(II) de tipo metalaciclofano obtenidos a partir del autoensamblaje de ligandos aromáticos oligo_p_fenilenos ú oligoacenos con iones CuII. This leads to heart metalacíclico type metalaparaciclofano or metalaacenofano, with an orientation perpendicular between baseline levels of copper and spacers aromatic, and interactions? _? Among the latter. These oxamatocomplejos dinucleares copper (II) are role models for the study of the mechanism of interaction of electronic exchange through extended bridges. The variation in the nature of the spacer in these complexes has permitted a systematic study of the influence of different factors such as shape or topology ligand bridge in the magnetic properties of the compound final. This chapter presents an experimental basis accompanied by some theoretical predictions about the long-range magnetic coupling through bridges aromatic extended? _conjugados In complex dinucleares copper (II) type metalaciclofano. In Chapter II have synthesized two new sets of complex oligonucleares (di_ and trinucleares) metalosupramoleculares meso_helicatos double and triple thread from self-assembly of ligands linear oligooxalamidas politópicos (di_ and tritópicos) through metal ions from the first series of transition (CuII, NiII, CoII) with geometries preferential coordination. These two new families have enabled a systematic study of the influence of variation in the electronic configuration of the metal in the magnetic properties. The overall observed ferromagnetic behavior is due to the rotation of the spin density in the spacers phenylene with replacement goal, as evidenced by the theoretical calculations DFT, which corroborates the general validity of the spin polarization mechanism for the spread of the interaction redemption in metal complexes. In chapter III has synthesized a series of complex polynuclear both homo as heterobimetálicos of different nuclearidad, tetra, hexa- and octanucleares structured type of dímero dimers, dímero of trímeros and dimers of tetrámeros respectively. The synthetic strategy in the preparation of these polynuclear complexes is based on the methods of self-assembly scheduled, which allows different parameters vary synthetics (such as the nature of the ligand oxamato and ligand-blocking, metal ions, contraiones, etc.). The two new families of complex hexanucleares M2M'4 and octanucleares M2M'6 (M = Cu, Ni, Co, M '= Cu, Ni, Co, Mn) provided several examples of SMMs, thus permitting study the role of spin and the magnetic anisotropy in the phenomenon of magnetic relaxation slow. This family of chains heterobimetálicas provides several examples of magnet chains (SCMs) and allows to study the influence of various factors such as metal ion anisotropy local MII or the number, size and position of the substituents on the aromatic ring of ligand oxamato in the dynamics of magnetic relaxation slow.

Author: Mato Iglesias Marta Maria.
Year: 2005.
University: A CORUÑA.
Place of defense: Facultad de Ciencias.
Place of preparation: Facultad de Ciencias.

Summary: Currently, the Magnetic Resonance Imaging (MRI) is one of the non-aggressive diagnostic techniques most useful in medicine. The magnetic resonance imaging are based on the signal intensity of the proton NMR of water molecules in tissues and today is the usual use of contrast agents for imaging high quality. The success of these products, along with the rapid development of the technique of RMI, demand a new generation of contrast agents more effective and selective. In this line, this Doctoral Thesis has been aimed at the design, synthesis and characterization of new chelates of lantánidos with potential application as a contrast agent in MRI. This has been designed four new ligands octadentados and has studied its ability to coordinating ions lantánidos. The four-designed receivers have in common the presence of two units acid 6 - (aminomethyl) piridina-2-carboxílico in their skeletons, and they differ in the spacer used between the two units (a group methyl, ethyl, propyl or ciclohexilo), as well as the presence of carboxylate groups phosphonate or its structure. The objective of these structural changes has been to study the effect of the rigidity of the ligand and compression estérica about ion lantanido on the parameters that determine the relaxividad in the corresponding complexes Gd3 + Based on structural considerations, it has been able to control rationally the exchange rate of the water molecule coordinated in this family of chelates. This is an important factor that must be optimized to obtain new contrast agents more effective. The structure of the chelates in solution has been studied using a wide variety of spectroscopic techniques, as well as estimates of quantum mechanics. In the case of chelates of Gd3 +, the long time relaxation electronic ion prevent any presents this observation in the NMR spectra of high resolution, so that its structure in solution should be deducted from the structure of chelates with other similar lantánidos. Here, the theoretical calculations can provide firsthand information systems Gd3 +, including dynamic processes too fast to be observed in the NMR time scale as the sharing of the water molecule coordinated. Furthermore, the calculations on molecular clusters have provided useful information to establish the second area of hydration, which in turn, has been shown to increase the relaxividad in chelates of Gd3 + containing phosphonate groups.

Author: Chas Pedreira Marcos.
Year: 2005.
University: A CORUÑA.
Place of defense: Facultad de Ciencias.
Place of preparation: Facultad de Ciencias.

Summary: The thesis is divided into two parts. The first one deals with the collection of receivers rectangular metalocíclicos autoensamblados centers metallic Palladium (II) and platinum (II). The skeletons of these receptors composed, in the sides of the rectangles, ligands bidentados groups viológenos mono or dicuaternizados, 3 - or 4-alquilpiridinas and, in some cases, phenylene groups. The "edges" of the rectangle formed groups -CH2- and metal centers themselves. The strategies used to carry out the autoensamblajes include strict thermodynamic self-assembly and directed self-assembly through an anion template. The metalocilcos obtained were characterized by nuclear magnetic resonance and mass spectrometry of low resolution and in the case of metalociclos Platinum (II) too high resolution giving in all cases results sastifactorios. Once obtained receivers metalocíclicos, studies the complexion of organic substrates by them. Due to the size of the cavities that have and the nature of elos structural elements that form, concludes that the molecules or ions groups aromatic substrates are ideal for our receivers. The study provides one hand, the interactions between receptor and substrate and structural aspects of inclusion complexes, using nuclear magnetic resonance. On the other hand, we studied by UV-Vis spectroscopy, the balance for the inclusion of organic substrates recipients, by calculating the equilibrium constant for the same water and in an organic solvent such as nitromethane. The second part of the thesis deals with the self-assembly, also centers metallic Palladium (II) and platinum (II) [2] and [3] - catenanos combining metalociclos with macrociclos entirely organic. The [2] -catenanos are based on two of the metalociclos obtained in the first part of the work in combination with the macrocycle 1,4,7, 10, 13, 20, 23, 26, 29, 32-decaoxa [13.13] paraciclofano . The study of these structures by nuclear magnetic resonance gives us information on the nature of the interactions between the two linked and even relative motions of the same. Finally, it is the self-assembly of [3] -catenanos through metal centers Palladium (II). In this case we used a different type of ligands to the past and a complex of Palladium (II) in trans. In addition to ligands with groups bipiridinio monocuaternizados, it also makes use of another ligand with 2,7-diazapireno monocuaternizado, which offers greater efficiency in the process of self-assembly. It also explores the influence of perfuoración one of the rings of macrocycle organic part of the catenanos the effectiveness of the process of self-assembly.

Author: GALET DOMINGO ANA GUADALUPE.
Year: 2005.
University: POLITÉCNICA DE VALENCIA.
Place of defense: UNIVERSIDAD POLITÉCNICA DE VALENCIA.
Place of preparation: UNIVERSIDAD POLITÉCNICA DE VALENCIA.

Summary: The research presented in this thesis is focused on the coordination chemistry of ions Fe (II) and Co (II) with a variety of ligands with nitrogen atoms giving unsaturated metal and cyanide. This thesis is organized into two parts: the first part presents the structural characterization and study of the magnetic properties of systems of Fe (II) and Co (II) spin transition. The compounds with transition from spin states are switchable between two competing thermodynamics: the state of spin and high spin state low. Both states differ in their magnetic properties, optical and structural. The change of status can be stimulated by a change in temperature, pressure or irradación with light. In general, the existence of elastic interactions comparative home creates a transition from spin discontinuous nature and sometimes with hysteresis which gives effect to these systems memory. The first chapter is an overview of spin transitions: background and current situation, conceptual definitions, relevance and interest generated. The second chapter presents a study of the effect of contraiones and solvent molecules in the spin transitions. To do this we conducted the comprehensive study of the system of Co (II) with the ligand 2,6-bis (2-piridil) -4 (1H) -piridona. This study gives a variety of crystalline structures and magnetic properties of compounds that include high-spin, spin compounds with transition to a greater or lesser cooperatividad compounds and low spin. The third chapter examines the transition from spin compounds heterobimetálicos Fe (II) - [M (CN) 2] (M = Cu (I), Ag (I) and Au (I) with a variety of organic ligands type pyridine replaced (3-CNpy, 3-Fpy, 3-Clpy, 3-Brpy, 3lpy, 3-NH2py) getting a large amount of crystalline structures one-dimensional, two-dimensional and three-dimensional magnetic responses to a wide variety ranging from very cooperative transitions spin up compounds spin around the high-temperature range. This chapter includes the study of the effect of pressure on the transition from spin on some of the compounds presented. The second part presents a new solid electrolyte based on ions Fe (II) , 1,10-fenantrolina-5 ,6-diona and Na + ions, contraiones CIO4 and water molecules. measures conductivity conducted on monocrystals have shown that this compound is an efficient ion driver even at temperatures below 163 K.

Author: CASANOVA I CASAS DAVID.
Year: 2005.
University: BARCELONA.
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA - UNIVERSIDAD DE BARCELONA.

Author: FERNÁNDEZ RECIO LUCÍA.
Year: 2005.
University: SANTIAGO DE COMPOSTELA.
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The main content of the thesis is the synthesis of new clusters of copper (I) with atoms calcógenos as bridges íntermetálicos stabilized, in most cases, with various fosfinas. Compounds obtained can be classified into three different groups, according to the characteristics of clusters obtained. The first group of compounds contain a kernel of selenide copper (I) surrounded by a layer of copper sulfide (I) and have formulas: [Cu17Se (SPh) 15 (PPh3) 4] (1) [Cu20Se (SPh) 12 (OAc) 6 (PPh3) 4] (2) [Cu28Se6 (SPh) 16 (PPh3) 8] (3) [Cu36Se8 (SPh) 20 (PPh3) 8] (4) [Cu54Se8 (SPh) 30 (OAc) 8 (PPh3) 6] (5) [Cu72Se14 (SPh) 36 (OAc) 8 (PPh3) 6] (6) The second group of compounds consists of clusters of copper (I) with bridges calcógeno stabilized by ligands bidentados with atoms giving N, S and formulas are: [Cu4 (S-tia) 4 (PPh3) 2] (7) [Cu4 (S-tia) 4 (PEt2Ph) 2] (8) [Cu4 (S-tia) 4 (PEt3 ) 2] (9) [Cu4 (S-tia) 4] 2 (10) [Cu4 (S-tia) 4] 4 (11) [Cu4 (S-tia4]? (12) [Cu16Se6 (S-bztia) 4 dppm4] (13) [Cu50Se24 (S-tia) 2dppm 10] (14) [Cu48Se24 (HS-tia) 2dppom10] (15) and [Cu2 (HAm4DM) 2Cl2] (23). The third group is composed of compounds clusters of copper (I) with ligands tiolato para-funcionalizados and have formulas: [Cu4 (S? NO2) 4 (PPh3) 4] (16) [Cu4 (S? NO2) 2 (Oac) 2 (PPh3) 4] (17) [Cu22Se6 (S? NO2) 10 (PPh3) 8] (18) [Cu36Se8 (S? NH2) 20 (PPh3) 8] (19) [Cu6 (S? NH2) 2 (S? NH3) 2dppm4] [OAc] 4 (20) [Cu6S2 (S? NH2) 2dppm4] (21) [Cu6Se (S? NH2) 2dppm4] (22). Once obtained, all clusters are crystallized and their structures were determined by dfractometría ray X monocristal. were also studied the optical properties for the compounds most significant poniéndos clear that the intensity of color clusters increases with the size of the same and with the presenciqa of amino or nitro groups as substituents on the ligands funcionalizados. Also explored limuniscencia of the most significant clusters can establish correlations depending on the ligands funcionarizados used.