COORDINATED COMPOUNDS (2)

Author: ALARCÓN PAYER CAROLINA.
Year: 2005.
University: GRANADA [www.ugr.es].
Place of defense: FACULTAD DE FARMACIA , UNIVERSIDAD DE GRANADA.
Place of preparation: FACULTAD DE FARMACIA, UNIVERSIDAD DE GRANADA.

Summary: This research provides the synthesis and structural study (Crystallographic) and properties (thermal, spectral and / or magnetic), 17 new compounds with a mixture of ligands containing copper (II) as a focal point, EGTA chelator dinucleante and as a nitrogen heterocycle as a ligand assistant. The crucial support of the conclusions derived from the results cristalográficos, but also makes a notable effort to establish correlations of infrared spectroscopy primarily associated with the band tension antisymmetric of cromóforo COC for the functional group ether. It establishes a general nature, without exception, each semiligando EGTA takes the shape mer-NO2 + O (ether, apical) in the chelate Cu Cu (mu2-EGTA) when the ligand is assistant aqua (the parent compound) or heterocycle nitrogen that contributes to the giver metal center in a proportion 1:1. This is the case in a series of 12 compounds where the ligand imidazólico or piridínico incorporates a N-heterocíclico each center cash. Moreover, it also establishes without exception that the incorporation of two N-heterocíclicos each center cash induces a change conformacional so that every semiligando EGTA acts as a chelating tetradentado tripod in shaping NO + O (carboxylate, apical) + O (ether , apical). This provides for 5 compounds and new is in line with what contributed to the literature for a single bibliographic direct antecedent where the ligand assistant for each of the metal centers, is ethylene diamine. The parent compound and a molecule containing similar creatinine united to each center show the metallic copper index coordination 5, while three similar compounds containing copper penta and hexa-coordinado and 8 others have only centers metallic hexacoordinados. The compound where the ligands or auxiliary contribute two nitrogen giving each metal center are all hexacoordinados and, without exception, show an environment type 4 +1 +1 where the link Cu-O (ether, apical) is the longest.

Author: BERNECHEA NAVARRO MARÍA.
Year: 2005.
University: LA RIOJA [www.unirioja.es].
Place of defense: UNIVERSIDAD DE LA RIOJA.
Place of preparation: UNIVERSIDAD DE LA RIOJA.

Summary: The work entitled "Synthesis, characterization and reactivity of new organometallic compounds of metals group VIII with ligands alquinilo or fosfinoalquino" is divided into three different sections. - The first is the preparation and study of the reactivity of isomers, electronically different trans-hidruro-acetiluro-platino (II) complexes and acetylene platinum (0), with ligands trifenilfosfina compared to the kind disolvatada of platinum cis-bis (pentaflurofenilo) bis (tetrahydrofuran) platinum (II). - The second part focuses on the synthesis and characterization of new species mononuclear ion d6 and d8 (rhodium, iridium and ruthenium) with ligands alquinilfosfina, rare in the literature and the study of their reactivity. - Finally, is the synthesis and characterization of new compounds trans-di (chlorine) tetra (alquinilfosfina) ruthenium (II) and the study of their reactivity face alquinos terminals and its potential as a precursor of type catalytic reactions ROMP.

Author: RUBIO MORENO MIGUEL.
Year: 2005.
University: SEVILLA [www.us.es].
Place of defense: INSTITUTO DE INVESTIGACIONES QUÍMICAS.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS.

Summary: This Doctoral thesis is divided into two separate chapters. In the first of them, have synthesized a new set of ligands fosfina-fosfito complementing other synthesized previously in the group, which has been modulated structure fragments Phosphine and fosfito. Furthermore, it describes its application in various processes catalytic enantioselectivo. The implementation of the ligands fosfina-fosfito 9 in the hydrogenation enantioselectiva of a-aciloxifosfonatos 11, has resulted in efficient catalysts for this reaction, which operate with levels enantioselectividad of up to 98% ee. The NMR studies conducted with the complex formulation [Rh (P-OP) (11a)] + olefine show that the preferred position of cis coordination to fosfito. The proximity between fosfito and olefine causes coordinated activity of the catalysts depends markedly volume estérico of substituents of biarilo. Studies on the hidroformilación asymmetric of styrene, catalysed by species rhodium modified with ligands fosfina-fosfito, have revealed a significant influence on the structure of both ligand activity in the enantioselectividad of reaction. The system consists of the ligand 4g has provided the best result in enantioselectividad (71% ee). The latest application has been studied catalytic adding conjugate of ZnEt2 to 2-ciclohexenona catalysed by copper species that has given rise to do catalysts that operate with a level of enantioselectividad moderate. In this study, has been isolated and characterized the precursor catalyst formulation [Cu (MeCN) 2 (5c)] BF4 that demonstrates how coordination bidentado of ligand. In the second chapter, has developed a method of synthesis suitable for the preparation of the new ligands difosfito type pincer 30 and 31, based on the reaction between an aromatic diol and two equivalents unc lorofsfito, in the presence of a base. This procedure allows synthesize ligands diffosfito quierales using a clorofosfito chirality. The characteristics of the NPP and PCP ligands allow their coordination to mental mode coordination pincer. We have synthesized a family of rhodium complexes containing addition to the above, other lgiandos L, such as PPh3, CO, C2H4, CNXy MeCN. The behavior of the p acceptor ligands difosfito leads Jan l center a notable deficiency electronic cash, which is reflected in the IR spectra of the complexes 35 and 36. Studies of X-ray diffraction conducted sobrelos compounds 37 and 41 reveal parallel coordination of the unity of C2H4 the level of coordination of the molecule. This provision has not been previously described in compound analogues rhodium (I) with square plane geometry.

Author: GARCÍA MARTÍN JAVIER.
Year: 2005.
University: JAÉN [www.ujaen.es].
Place of defense: FACU. DE CIEN. EXPERI. Y DE LA SALUD.
Place of preparation: FACULTAD DE CIENCIAS EXPERIMENTALES Y DE LA SALUD.

Summary: The results presented in this paper is directed towards the design of a method funcionalización specific to the surface of activated carbon, in order to optimize its capacity as host of metal ions, based on the anchor formed by molecular modeling a fragment arómatico, with a capacity of anchored to the centers arénicos coal through interactions type pi-pi and an aliphatic rest with core groups suitable for the retention of metal species. In this regard have been synthesized compounds AMNLYSH2 and AMNTRENH, and has done the structural and chemical characterization of the same by deepening their behavior as ligands compared to metal ions in aqueous solution. On the other hand, explored the textural characteristics of commercial activated carbon chosen for this job, and it was determined the nature of the functional groups and the behavior of the surface acid. Subsequently, the compounds AMNLYSH2 and AMNTRENH is adsorbieron on activated charcoal Check the mechanism of interaction is highly irreversible, based on the results obtained from adsorption isotherms of the same at different pH values, molecular orbital studies both the adsorbent and the two adsorbatos and XPS data. Finally, we assessed the ability as adsorbents systems carbón-ligando by analyzing the corresponding adsorption isotherms of a series of metal ions from industrial interest and / or environmental, and comparing the retention capacity of the latter on adducts carbón-ligando and coal mentioned at the outset.

Author: GONZÁLEZ MARÍN ANA ISABEL.
Year: 2005.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The results presented in this report confirm that the complex Os (h5-C5H5) Cl (PiPr3) 2 is a product of extraordinary departure for the development of the chemistry of the unit osmium ciclopentadienilo. The presence of two links labile (Os-Cl and Os-P) make this a precursor derived very versatile, which has enabled the study of a wide variety of activation and coupling reactions. We have prepared osmium complexes carbeno of Os (h5-C5H5) Cl (= CHPh) (PiPr2R) (R = iPr, - C (CH3) = CH2), which show an ambivalent behavior of Fischer and Schrock, as they react to nucleotide and electrófílos. The reactions of both compounds with nucleotide C-dadores lead to links carbono-fragmento organic. However, there are marked differences in the nature of the products resulting from the addition of H +, which depends on the replacement of the R Phosphine. Thus, while the reaction of the complex triisopropilfosfina H + leads to a derivative h3-bencilo, the addition of H + to compound isopropenildiisopropilfosfina leads to a derivative hidruro-bencilciclopentadienilo. Reactions with TIPF6 lead to derivatives hidruro-carbino. These complexes, desprotonación with metóxido sodium generate species neutral Os (h5-C5H5) (CPh) (PiPr2R) (R = iPr, - C (CH3) = CH2), which in the presence of methanol lead to products coupling carbono-oxígeno by adding the liaison OH alcohol triple link Os-C of carbino. The unit osmio-ciclopentadienilo is also an appropriate medium for the formation of fosfinas funcionalizadas. The ligand a-alquenilfosfina complex Os (h5-C5H5) CI (= CHPh) (PiPr2 [C (CH3) = CH2]) becomes a a-alilfosfina through an intermediate osmafosfabiciclopentano through a reaction cicloadición [2 +2] CC double bond between the phosphine and the double bond Os-C of carbeno. The transformation osmafosfabiciclopentano-alilfosfina shows that in the presence of a vacant coordination in the metalaciclo favors the process of b-eliminación hydrogen compared to metátesis. The insertion of the triple link NPP benzonitrilos a link C (sp2) - H leads to the phosphine compounds iminofosfina. These species, in the presence of borohidruro sodium and methanol, are breaking the link PCs to units osmapirrol. The metal fragment [Os (h5-C5H5) (PiPr3)] + is also a useful template to promote the formation of species alilo d6 and d4, using carbon-carbon coupling of a ligand and vinylidene nucleotide carbonised, which contain atoms hydrogen atom in the giver, and the subsequent activation of a link CH. The ligands alilo in these compounds are coordinated in ways exo and endo. The mode of coordination ligand alilo depends on the electronic structure of metal as a center of the substituents of alilo syn respect to the proton Hmeso. While ions d6 foster coordination exo, the relative stability of isomers exo and endo species d4 is governed by the substituents at position syn.

Author: ESCORIHUELA VITALES MARÍA INMACULADA.
Year: 2005.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS-ICMA.

Summary: The work has been based on the use of forces no-covalentes in coordination chemistry. This thesis shows that these forces can be used as a probe to select products with different characteristics in the laboratory. In the first chapter "Modulation effect pseudo-Jahn-Teller in complexes of Cu (II) in solid-state" explores the influence of subtle changes in the molecules forming the coordination crystalline compound, using as a probe the effect pseudo-Jahn - Teller. In the second chapter on "Studying the interactions Intermoleculares the behavior of complex Cu (II) and Pt (II) with the ligand CN," used these fuerzs to get complex with varying degrees of nuclearidad within similar chemical systems. In addition, one of them is an intermediate in the formation of the classic type chlathrates Hofmann. The third chapter, "Zn complexes with ligands Uracilato, Timinato, 6-Metiluracilato and 5-Fluorouracilato" covers the joint study of the influences of changes in shape and size and the formation of hydrogen bond and / or electrostatic interactions ligands interest in biology (Uracilo and Timina part of nucleic acids) and medicine (3l 5-Fluorouracil is used as an antineoplastic in various types of cancer for more than 40 years) in coordination compounds Zn. The differences between the topological ligands have led to a comparative study in depth.

Author: RODRÍGUEZ MARTÍNEZ M. DEL CARMEN.
Year: 2005.
University: VIGO [www.uvigo.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: UNIVERSIDAD DE VIGO.

Summary: In this paper analyzes the interaction of ruthenium precursors with different ligands difosfinito [1,2-bis (difenilfosfinoxi) ethane, (I)] and diaminodifosfino [N N'-bis (difenilfosfino) - N, N'- ( dimetiletilendiamino) (LN)]. As ruthenium precursors have been used [RuCl2 (DMSO) 4], RuCl3.3H2O and [RuCl2 (THF) (CO) 3]. In the first chapter of the thesis presents the results obtained from the complex [RuCl2 (DMSO) 4]. The reaction of this complex with lingado What gave rise to various complex monkey and dinucleares depending on the relationship estequiométrica employed. We have isolated and characterized complexes [ru (u-Cl) 3 (MSO) 3Cl (I)] (1), [Ru (u-Cl) 3 (DMSO) Cl (I) 2] (2), [( RuCl (n2-Lo) (n1-Lo (O))) 2 (u-Cl) 2] (3), [(RuCl (I) (L ')) 2 (u-Cl) 2] (4), [(Ru (I) (L ')) 2 (u-Cl) 3] + Cl (5), [Ru (Cl) 2 (I) (L') 2] (6), [RuCl2 (Lo) (Ph2POPPh2)] (7) and [Ru-Cl (P) (I) (Ph2POCH2)] (8), where L 'represents a ligand fosfito monodentado. In Chapter 2 presents the results obtained by the carbonilación of solutions RuCl3.3H2O and subsequent reaction with ligands Lo and LN. We have isolated and characterized different clorocomplejos of ruthenium (II), whose subsequent treatment with LiAlH4 or NaBH4 led to new hidrurocomplejos of withheld (II). In Chapter 3 presents for a party, the results of the reaction of [RuCl2 (THF) (CO) 3] with Lo, which originated obtaining new complex dinucleares of ruthenium (II). Moreover, from this precursor of ruthenium, has designed a new method of synthesis of species of Ru (0) [Ru (CO) 2 (PR3) 3] much easier and faster than methods used so far this and that allows synthesize complex general formula [Ru (CO) 2 (L) 3] (L = PPh3, PPh2Me and PnBu3) and [Ru (CO) 2 (PR3) (DB)], where DB represents a ligand phosphide bidentado.

Author: MALDONADO ROGADO MARÍA AMPARO.
Year: 2005.
University: EXTREMADURA [www.unex.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS, DEPARTAMENTO DE QUÍMICA INORGÁNICA, UNIVERSIDAD DE EXTREMADURA.

Summary: 1.1. INTRODUCTION hetero atoms containing nitrogen or sulfur can be found in the structure of many natural products and pharmaceutical compounds. In addition, they can be part of ligands multidentados used very often in the chemistry of coordination with the goal of obtaining new compounds having bioactivity. These ligands are derived from indazol, benzimidazole, tiazina and thiazoline. Thus, some derived from tiazina present anti-tumor properties, antihistamine anti-inflammatory, analgesic and antibiotic. Similarly, some derived from thiazoline are interesting also because of their potential activity as antibiotics and anti-tumor agents. Similarly, indazol and its derivatives are of considerable importance from the point of view of its promising pharmacological properties. Finally benzimidazol and its derivatives are widely used for its activity antiparasitaria, antifungal, and antiviral allergic. Interestingly, coordination makes bioactive ligands increase their capacity, and that ligands inactive acquire propendes pharmacological interventions. For examples derived from 2-aminobencimidazol with metals such as cobalt, zinc and copper showed antibacterial and antifungal activity and ruthenium are cytotoxic. In addition, benzimidazole, as a ligand compared with transition metal ions, also has a keen interest due to complex metal salts with this ligand have been widely studied as models of some important biological molecules. Because of the importance of this hetero in the pharmaceutical development, we hemosiniciado a line of research on the chemistry of coordination compounds containing rings tiazina, thiazoline, indazol and benzimidazole with metal ions of the first series of transition.

Author: LOZANO VILA ANA MARÍA.
Year: 2005.
University: EXTREMADURA [www.unex.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENICS, SECCIÓN QUÍMICAS DE LA UNIVERSIDAD DE EXTREMADURA.

Summary: The tiazolinas, tiazolidinas and tiazinas are hetero present in a large number of substances with biological properties. The tiazolinas can act as pharmaceutical agents, and biologically active natural products such as antibiotics, inhibitors of HIV or antiproliferative agents [1-5]. In addition, the ring 2-tiazolina is part of the structure of some sideróforos as Pioquelina [6] and Desferritiocina [7]. Moreover, the thiazolidine ring is present in the structure of penicillins [8]. Likewise, the hetero-1,3-tiazina part of the skeleton of cephalosporins [9], a family of antibiotics beta-lactámicos who base their mechanisms of action of inhibiting the synthesis of the bacterial cell wall [10] , as well as the penicillins, which also belong to this family of antibiotics. In turn, some drifts of 1,3-tiazainas presented properties anti-inflammatory, analgesic and antipyretic comparable to aspirin [11.12], as well as anti-tumor properties, antiviral `13], anticoagulants, antimalarial [14] and antiimcobacterianas [ 15]. Furthermore, it has been shown that the corresponding coordination compounds can influence the biological activity of these substances, in some cases potenciándola significantly [16]. These ligands were as follows:-2 - (3,4-diclorofenil) imino-N- (2-tiazolin-2-il) thiazolidine (TdTn) - 2 - (3,4-diclorofenil) imino-N- (4H- 5.6-dihidro-1 ,3-tiazín2-2il) thiazolidine (TdTz) - 2 - (3,4-diclorofenil) imino-N- (4H ,5,6-dihidro-1 ,3-tiazín-2-il ) tetrahidro, 1, -tiazina (TzTz) - 2 - (3,4-diclorofenil) imino-N-2-tiazolín-2-il) tetrahidro- 1,3-tiazina (TzTn). The synthesis of ligands derived described below: ligand TdTn was obtained by 3 ways different synthesis in order to increase significantly its performance. The first time was reaction 3,4-dicloroanilina with 2-cloroestilisotiocianato in a process now stirring Cold reflux and agitation at room temperature reaching the 16 hours. The other two were made with synthetic common the last step reaction among the precursor 2 - (3,4-diclorobencilamino) -2-tiazolina and 2-cloroetilsotiocianato. One way of obtaining this was based on pioneering do react, as a first step, 2-mercaptotizaolina with methyl iodide, extremándose precautions in the handling of the second reagent because of its potent toxicity. The last step in this process was to obtain the precursor to basic means for the dissolution of yodhidrato of 2 - (3,4-diclorobencilamino) -2-tiazolina which was obtained until the emergence of a solid white. The second route of synthesis of the precursor was based, first, on the reaction between 3,4-diclorofenilisotiocianato with ethanolamines to obtain tiourea. The continuation was reacting this tiourea acid clorhidríco warming at reflux for 3 hours. Finally, we obtained the precursor 2 - (3,4-diclorobencilamino) -2-tiazolina carrying basic means the resulting dissolution. The second ligand, TdTz, was synthesized by reacting the precursor 2 - (3,4-diclorobencilamino) -2-tiazolina obtained in two ways above, 3-cloroporpilisotiocianato warming at reflux for 4 hours. In the case of ligand TzTz used 2 channels of obtaining dif 8 erentes 1ff8 to consider what enhanced his performance. In the first of these summaries was reacting 3,4-dicloroanilina with 3-cloropropilisotiocianato in a stirring Cold reflux, and agitation at room temperature for a duration of approximately 18 hours. The second track is to obtain step in the reaction between the precursor 2 - (3,4-diclorobencilamino) -2-tiazina and 3-cloropropilisotiocianato. To obtain this was a precursor reaction 3,4-diclorofenilisotiocianato with propanolamina to obtain tiourera. Subsequently, it was added to that tiourea dissolution acid clorhidríco warming at reflux for 3 hours. Finally, it got the precursor 2 - (3,4-diclorobencilamino) -2-tiazina decreasing acidity resulting from the dissolution. The fourth ligand achieved TzTn, was obtained by reacting the precursor 2 - (3,4-diclorobencilamino) -2-tiazina with 2-cloroetilisotiocianato heating the mixture for 4 hours and reflux. Once the solids obtained from the ligands, we proceeded to the crystallization of the same techniques of crystal growth by slow evaporation of the solvent, thereby finally crystal size and optical quality suitable for the X-ray diffraction of monocristal. He then proceeded to the determination of the crystal and molecular structure of the ligands by diffraction techniques, using the package program WinGX [17] for the resolution and refinement of crystal structures and the search program CONQUEST structures [18] , which provides the Cambridge Structural Database [19], for the comparative study of the existing structures. A diagram of the molecular structure of TdTn, TdTz, TzTz and TzTn, which has drawn the eplipsoides heat to a probability level of 50%, can be seen in Figures 1,2,3 and 4, respectively. In addition to characterize the ligands by X-ray diffraction of monocristal, were studied by other techniques such as elemental analysis, nuclear magnetic resonance of 1H and 13C, spectroscopy UV-visible and spectroscopy UV-Visible and IR spectroscopy. It is worth mentioning that all these ligands have the potential to form chelate rings of six members, which are particularly stable. This to assume that systems metal / ligand studied compounds could be obtained coordination stable. Upon completion of the synthesis and characterization of ligands obtained, we proceeded with the preparation of the complex of cobalt, copper, zinc and cadmium in solid phase through reaction of each ligand with metal chloride. The next step was to continue the search for monocrystals complexes obtained, thereby, through techniques of crystal growth by vapor diffusion or slow evaporation of the solvent, crystals suitable for the technique of X-ray deification of monocristal of the complex [ CoCl2 (TdTn)], [CoCl2 (TdTz)], [CuCl2 (TzTn)], [ZnCl2 (TdTn)] and [ZnCl2 (TzTz)]. The crystals that did not attain sufficient size or quality were studied by optical ray diffraction Z dust. So, using methods of direct space through a search algorithm 'Monte Carlo / temperate parallel' implemented in the software package FOX [20] and applying the method of Rietveld [21] for refinement, we determined the crystal structure of the complex [CuCl2 (TdTn)], [CuCl (TdTz)] (isomer coordinated by the N tizaínico) [CuCl2 (TdTz)] (isomer coordinated by the S tiazínico) [ZnCl2 (TdTZ)], [ZnCl2 (TzTn )] and [CdCl2 (TzTn)]. Apart from determining the molecular structure of crystalline solids and isolated by diffraction techniques, continued characterization of the complex obtained by elemental analysis, mass spectrometry, spectroscopy, IR spectroscopy electronics, electronic spin resonance and magnetism. In all cases, it was concluded that the structure of the complex was distorted tetrahedral, with the metal atom attached to two ligands and a chlorine molecule ligand (TdTn, TdTz, TzTz or TzTn) that behaves as didentado and coordinates the central ion through atoms of nitrogen tiazolínico and imínico (if it's TdTn or TzTn), or tizínico and imínico (in the case of TdTz or TzTz), forming a ring chelate six members. The only significant difference was found in one of the isomers of the complex [CuCl2 (TdTz)], which co-ordinated by the atom sulfur tiazínico (and not by the nitrogen in the same ring). To check possible biological properties and / or of pharmacological compounds synthesized, it proceeded to the study of biological ligands and complex obtained, considering the remarkable interest that this area is presented in the field of chemistry boinorgánica for his involvement in aspects the mode of action of metal ions in living systems, toxicity, medication use, and so on. The biological tests conducted consisted of: A-Studies of the antimicrobial activity of the compounds synthesized in front of various microorganisms. Analysis of the results indicated that only four complexes showed a certain degree of antimicrobial activity on the growth of some of the strains: [CoCl (TzTz) 2], [CuCl (TdTn) 2], [CuCl (TdTz) 2] (isomer coordinated by the nitrogen tiazínico) and [CuCl (TzTz) 2]. B-Studies of the influence of the organic ligands and complex in the phagocytic activity of human neutrophils (preceded by appropriate evidence of viability). In regard to the phagocytic activity, as shown in Figure 5, the index rose or phagocytic ability of neutrophils to swallow bags of latex to treat the samples with different compounds, except in the case of ligand TdTz, not seemed to produce any evidence regarding this aspect. The increase mentioned was statistically significant (P less 0.05) in the case of cells treated with the complex [CuCl (TzTz) 2] compared with the control and the samples treated with the three organic ligands and the complex [CuCl ( TdTz) 2] and [ZnCl (TdTn) 2], as well as for neutrophils in the presence of complex [CoCl (TzTz) 2] when compared with control and the three ligands. Also, in the case of a percentage phagocyte (Figure 6), there was a statistically significant increase (P less 0.05) when neutrophils were incubated with the complex [ZnCl (TzTz) 2] compared with the control sample, which that means there are more cells activated. Finally, the phagocytic efficiency (Figure 7) was higher in neutrophils two deals with the complex, but not in the case of ligands, which remained unchanged or even declined. This efficiency was significantly greater (P less 0.05) that the values of control, the ligands and the complex [CuCl (TdTz) 2], [ZnCl (TdTn) 2] and [ZnCl (TzTz) 2] in the case of the sample treated with the complex [CuCl (TzTZ) 2]. In turn, the complex [CoCl (TzTZ) 2] also introduced an increase in phagocytic efficiency statistically significant (P less 0.05) compared with control and ligands. Finally, the values of phagocytic efficiency of genetic crops conducted in the presence of complex [CuCl (TdTn) 2] were statistically significant (P less 0.05) compared with the samples treated with the ligands TdTn and TzTz. From the results it can be concluded that most compounds that increase the ability of phagocytic leukocytes neutrophils in this study are complex [CuCl (TzTz) 2], [CoCl (TzTz) 2], [ZnCl (TzTz) 2] and [ CuCl (TdTn) 2]. This effect to promote phagocytosis (reflected in the phagocytic index) is due both to an increase in the number of phagocytes activated (phagocytic percentage) and the increased efficiency of these cells active fagocitar particles antigenic (phagocytic efficiency). Furthermore, it demonstrates that coordination to metal ions increases the role of neutrophils, increasing the record dive 8 uneinnat 27b not specific, since all three parameters phagocytosis assessed values presented above in the case of the samples treated with you complexes with regard to the same only incubated in the presence of the respective ligands.

Author: MORANTE ZARCERO SONIA.
Year: 2005.
University: REY JUAN CARLOS [www.urjc.es].
Place of defense: ESCUELA SUPERIOR DE CIENCIAS EXPERIMENTALES Y TECNOLOGÍA.
Place of preparation: UNIVERSIDAD DE ALCALA.

Summary: In this paper we develop new analytical methods for determining chirality of expóxidos obtained in asymmetric synthesis processes and their application to the study of the catalytic activity of a number of new complexes titatino (IV) with voluminous chiral ligands. The analytical methods developed are based on phase HPLC with chiral CHIRALPAK-AD-H in stationary phase standard for determining the enantiomeros of fenilglicidol. HPLC-MS also chiral CHIRALPAK-AD-Hy in stationary phase routine phase for the determination of the enantiomers of glycidol and capillary electrophoresis to determine lso enantiomers of fenilglicidol with succinil-ciclodextrina as chiral selector. It also summarizes complex alcóxido titanium (IV) with ligands fenoxo-éteres bulky and explores their business processes epoxidación alcohol cinámico and alcohol alílico.

Author: BRANDI BLANCO MARÍA DEL PILAR.
Year: 2006.
University: GRANADA [www.ugr.es].
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: Among the numerous compounds coordination, there is a very comprehensive package that includes so-called complex mixture of ligands containing a metal atom that meets their environment with two or more different ligands. The study of one or other combinations always requires an essential structural support. In this regard, studies cristalográficos represent the most valuable tool for on the one hand, which is to establish a complex with a mixture of ligands and the other, in order to clarify the nature and extent of interactions in a complex of 'external field '. Consideration of this wealth of information reveals, in very general lines, the effects of stiffness conformacional this ligand, in its various forms, as well as a notorious versatility that, beyond the behavior of coordinating its forms protonadas (H2pdc and Hpdc-) and anion (pdc2-), even beyond his denticidad

Author: Crespi Serrano Laura.
Year: 2006.
University: AUTÓNOMA DE BARCELONA [www.uab.es].
Place of defense: Facultad de Ciencias (UAB).
Place of preparation: Universidad Autónoma de Barcelona.

Summary: That argument is framed in the field of homogeneous catalysis, particularly in the synthesis of chiral ligands difosfito and catalysts for subsequent use in hidroformilación asymmetric olefins and natural products that are precursors of drugs enantioméricamente pure as the (S) -Naproxeno or Ibuprofen. Until the early 90's only catalysts Pt/SnCl2 with difosfinas chiral, 7 atoms in the ring chelate, allowing get excesses enantioméricos important but the activity quimio- and regioselectividad were low. From 90 even though they have evaluated a large number of ligands for hidroformilación catalytic asymmetric only have been achieved very good results with rhodium and difosfito of Union Carbide Chiraphite (% ee = 90) and the fosfina-fosfito ( R, S) -Binaphos (% ee = 95), which form chelates of 8 members. Recently in our group were synthesized and studied the ligand difosfito (R) -ftabinfos, forming rings chelate 16 members with rhodium, contains a skeleton with a central piece spacer isoftálico and produces% ee> 70 in hidroformilación of vinilarenos. His diastereoisómero (S) -ftabinfos not form chelates and consequently produces only a marginal ee. This result indicates a cooperative effect between the ligand center estereogénico and fragment binaftílico. Being the first time you use a metalamacrociclo in a process estereoselectivo and have achieved good results, it was suggested the synthesis and study of various ligands with the same structure as (R) -ftabinfos but varying fragments. They have been obtained 8 new ligands, characterized and tested in the hidroformilación styrene (olefine aromatic) catalysed by rhodium complexes. Six of them structurally related to the (R) -ftabinfos and 2 consist of a skeleton of 4 carbons, tartaric acid derivative and a fragment fosfito binaftílico. With those obtubieron best results were tested in hidroformilación of natural products (anetol, estragole, safrole and isosafrol). There has been enantioselectividades of 54% in aldehyde branched beta on the safrole, although regioselectividad is 38% in this aldehyde. It has been studied by NMR multinuclear structure of the complex (RhH (CO) L (difosfito)) n (L = P; PPh3). The results show that of the ligands only (S) -Me4ftabinfos, is capable of forming stable chelates by mononuclear species, similar to (R) -ftabinfos, but not generate good enantioselectividades because it piece connector center estereogénico and then it creates an environment to form chiral catalyst with rhodium. We have also prepared complexes (PtCl2 (difosfito)) ny by NMR 31P has been determined that exist in solution as mixtures of products from different nuclearidades and estereoquímicas. These complexes have been tested using SnCl2 as co-catalizador in hidroformilación of stretch, obtaining excesses enantioméricos low (15%).

Author: GARCÍA FONTECHA ANA.
Year: 2006.
University: LA RIOJA [www.unirioja.es].
Place of defense: UNIVERSIDAD DE LA RIOJA.
Place of preparation: CENTRO CIENTÍFICO TECNOLÓGICO. UNIVERSIDAD DE LA RIOJA.

Summary: The work is presented, focuses on the study of organometallic compounds homo-and heteropolinucleares platinum with unsaturated groups such as fosfinoalquino or cyanide and has been divided into two different sections. - The first part focuses primarily on the reactivity of new compounds Pt (II) and Pd (II), which contain at least one ligand alquinil (or diinil) (diphenyl) phosphine, PPh2CÂ eighth CR, as opposed to species of Pt (II) cis- [Pt (C6F5) 2 (thf) 2] and Pt (0) [Pt (h2-C2H4) (PPh3) 2]. Moreover, with the aim of deepening the parameters that control certain processes ciclación of ligands alquinilfosfina, explores the different behavior experiencing some derived mononuclear Pt (II) subjected to thermal or photochemical processes. - On the other hand, the second part focuses on the synthesis, characterization and structural study of the optical properties of polymeric derivatives heteropolinucleares oligoméricos or stabilized by interactions Pt-Tl, obtained by reaction of derivatives mononuclear (NBu4) [cis-Pt ( C6F5) 2 (CN) (PPh2CÂ fourth CPh)], (NBu4) [cis-/trans-Pt (C6F5) 2 (CN) 2] and (NBu4) 2 [Pt (C6F5) 4] with salt thallium (I) TlPF6.

Author: VAIANA LEA MARIA.
Year: 2006.
University: A CORUÑA [www.udc.es].
Place of defense: Facultad de Ciencias.
Place of preparation: Facultad de Ciencias.

Summary: In this Doctoral Thesis has sought to deepen the study of coordination compounds of transition metals with receivers macrocíclicos. In particular, it has shown how the variation of the rigidity of the structure and changes in the topology and rigidity of the arms hanging in a receiver macrocíclico can do it imposes a certain coordination geometry of the metal ion, or that suits the demands coordinativas it. This will have selected six recipients who belong to the class of so-called structural ethers lariat, which are macrociclos derived from the crown ethers in that incorporate side chains containing atoms giving posed potential additional positions of coordination. All recipients under study remain as common feature simultaneous incorporation of atoms of nitrogen and oxygen as heteroatoms, although the number and distribution of them differed from one another. Essentially these differences are manifested in two aspects: i) the crown of that dervian (1,10-diaza-15-corona-5 or 4,13-diaza-18-corona-6), and ii) the nature of the side chains that incorporate (aniline, benzimidazole or salicialdimino). Thus, L1 L3 and H2 L5 derived from the crowning of minor denticidad and size (1,10-diaza-15-corona-5), while the remaining receivers do the 4,13-diaza-18-corona-6. In turn, L1 and L2 incorporate side chains with aniline groups, L3 and L4 incorporated into his arms benzimidazole groups, and H2L5 and H2L6 incorporate side chains containing groups saliciladimino. For its part, from the standpoint of their potential giver, the recipient L1 and L3 can act as ligands heptadentados N4O3, L2 and L4 as octadentados N4O4, L5 as nonadentado N4O5 and finally L6 as decadentazo N4O6. As metallic cations has worked with Mn (II), Co (II), Ni (II), Cu (II) and Zn (II). While recipients L1 and L3, show an optimal architecture to force heptacoordinación and environment bipirámide pentagonal, unusual metal geometry of the first series of transition, L2 and L4 have shown greater versatility can adapt to the preferences of each electronic metal coming also to enable the production of complex binucleares for Co (II), Ni (II) and Cu (II). Particularly interesting is the complex of Co (II) L2, introducing structural features that are reminiscent of the active center of the MAP of Escherichia coli and can be considered a model of the same structural. With receivers L5 and L6, in all cases have been obtained compounds binucleares, some of them with very interesting structural features.

Author: PEREZ CADENAS MARIA.
Year: 2006.
University: MURCIA [www.um.es].
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA.

Summary: This thesis describes the preparation and characterization study of the properties and reactivity fotofísicas the first installment of complex Pt (II) and Pd (II) with the ligand (fluoren-9-iliden) metanoditiolato and its derivatives 2,7-di - tert-butil- and 2,7-dimetoxi-sustituidos. The new compounds homometálicos platinum correspond to the general types bis (ditiolato) platinato (II) and ditiolatobis (ligand) platinum (II) (ligand = fosfinas, isocianuros, diiminas). It has also synthesized a family of similar complexes of Pd (II) with the ligand 2,7-di-tert-butil-sustituido, a series of complex heterometálicos of Pt / Au and Pd / Au, as well as some coordination polymers Pd / Au, Pd / Ag, Pt / Pt and Au / Ag. Inputs more importanes set out below. For the first time it has been observed oxidation of a complex type of anionic a (ditiolato) platinato (II) in atmospheric conditions or by reaction with ferricinio, resulting in a complex mixed Pt (II) / Pt (IV) unprecedented . It has prepared a ditioato complex dinuclear of Pt (II) and complex mixed ditioato / ditiolato of Pt (II) and Pd (II) for protonación of compounds dianiónicos a (ditiolato) metalato. It has obtained a series of complex heterometálicos aggregation units (triciclohexilfosfina) gold (I) complexes of the type a (ditiolato) metalato or ditiolato (diimina) metal (II) (metal = Pt, Pd). Likewise, it has been granted a series of coordination polymers Pt (II) and Pd (II) ions by aggregating Au or Ag (I) (I) complexes to a (ditiolato) metalato. Have been measured and assigned the absorption spectra of all soluble complexes and the emission spectra of all the complex luminescent. The main conclusions are: (a) In the case of anionic complexes and derivatives with fosfinas and diiminas, absorption and emission energies for charge transfer transitions are lower than those observed for similar complexes with ligands 1, 1-etilenoditiolato containing groups retiradores of electron density. This can be attributed to strong character electrodador of ligand (fluoren-9-iliden) metanoditiolato, which increases the energy of the HOMO in all cases, causing a decline in the energy interval HOMO-LUMO. (B) has been described for the first time the luminescence of a series of complex type ditiolatobis (isocianuro) platinum (II). (C) The complex ditioato / ditiolato of Pt (II) are a new type of cromóforo showing lunimiscencia the dissolution at room temperature. (D) It has been described for the first time the luminescence of complex Pd (II) with ligands 1,1-etilenoditiolato. (E) The coordination of units (triciclohexilfosfina) gold (I) complexes of the type a (ditiolato) metalato (II) and ditiolato (diimina) metal (II) (= metal platinum, palladium) gives rise to significant changes in its fotofísicas properties. The main effect is an increase in the energies of the transitions MLCT or transfer cargo to the diimina as a result of the decline in the energies of HOMOs mixed metal / ditiolato.

Author: CIRERA FERNÁNDEZ JORDI.
Year: 2006.
University: BARCELONA [www.ub.es].
Place of defense: UNIVERSIDAD DE BARCELONA.
Place of preparation: UNIVERSITAT DE BARCELONA.

Author: BOZOGLIÁN TATLIÀN FERNANDO.
Year: 2006.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAT DE QUÍMICA.
Place of preparation: UNIVERSITAT DE BARCELONA.

Summary: Valencia compounds mixed with cyanide bridges are known for many years while interest in discrete species with nuclearidad defined is much more recent. There are numerous examples in the literature of complex matales transitional bridges with cyanide because their properties are suitable for applications in molecular magnetism, electrochemistry and molecular electronics. In this work we have prepared a series of complex discrete mixed valence class II containing CoIII / FeII and bridges cyanide. For the synthesis has been used original strategy that involves a series of steps redoz and replacement. This would have produced complex dinucleares of general formula [(Ln Co. III (u-NC)) II Fe (CN) 5] - and trinucleares [(Ln Co. III (u-NC)) 2 Faith II (CN4] 2 + where Ln represents a ligand macrocíclico pentadentado. has been studied the effect produced by variations in ligands macrocíclicos used as inductive factors on the redox properties, acid and the band charge transfer of these metal-metal compounds. A an essential part of this thesis is the study cinético-mecanístico the reactions of oxidation using different oxidants of external field. Based on the activation parameters has been determined the importance of interactions specific link hydrogen in the reactions studied. was also have prepared species dinucleares oxidized Co III / Fe III that have made it possible to reduce the reaction and establish the formation of hydrogen peroxide as a product of this reaction and the creation of the formation of hydrogen peroxide as a product of this reaction as well as establish a more likely mechanism for the domestic sphere. Lastly, it has studied the chemistry of some of the species on solid supports. have been used to sensitize solar cells where it has been able to establish the effectiveness of the band charge transfer metal metal injection of electrons in TiO2. Lastly, lagoons species trinucleares have been encapsulated in a solid medium of SiO2, which has found that the complexes are held both physically and by interaction with the matrix. these systems has been noticed that it is possible to reproduce within this matrix redox behavior of the species in solution.

Author: MATEO PÉREZ ANA CONCEPCIÓN.
Year: 2006.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE DERECHO.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This report describes new derivatives semi-sándwuich of Ti (IV) with ligands ciclopentadienilo or indenilo possessing a replacement ethyl b-funcionalizado. It examines the behavior of sustituyente amiro, ether or phosphine ligands of these in the new complex preparations, both in solution and solid state. In addition, it was discovered a family of precursors titanium catalyst semi-sándwich of highly efficient and regioselectivos for hidroaminación intermolecular of alquinos. The reactions of the complex CpXTiCl3 (X = CH2CH2NMe2 (N), CH2CH2OMe (O), CH2CH2PPh2 (P)) and IndTTiCl3 (X = CH2CH2NMe2 (N), CH2CJ2OMe (O)) with 1.0, 2.0 and 3.0 equivalents MeMgCl lead the resulting mono-, di-and trimetilo CpXTiMeCl2, IndXTiMeCl2, CpXTiMe2Cl, IndXTiMe2Cl, CpXTiMe3 and IndXTiMe3 respectively. In solid state, the atom giver of replacement X lingado ciclopentadienilo or indenilo these ocmpuestos is weakly linked to the metal center and ready transoide a ligand methyl. At dissolution, the group giver dissociates itself and reaches the equilibrium between species hepta- and hexaxoordinadas. The molar fraction of the species decoupled increases as does the impediment estérico around the center and as cash decreases the affinity group giver in the chain towards the titanium atom (NMe2 greater oMe = PPh2). In line with this, the reactions of CpOTiCl3 with 3.0 equivalent PhCH2MgCl, PhMgCl and (p-tolil) MgBr lead to derivatives CpOTiR3, with the replacement ether free both in the solid state as dissolution, as happens in the complex arilóxido CpOTiX3 - No No (OAr) (X = Cl, CH3, n = 1-3) and the propargilóxido CpOTiMen (OCPh2C = CH) 3-n (n = 1.2). Unlike lso compounds mentioned above, the group giver in the chain alquílica in the complex amido-imido ((2,6-iPr2C6H3) NH) CpXTi (= N (2,6-iPr2C6H3)) (X = N, P) , remains at the center coordinated both in cash and in state dissolution. Derivatives trimetilo CpXTiMe3, CpTiMe3, IndXTiMe3, H4IndTiMe3 and IndTiMe3 have proved to be precursors good catalyst for hidroaminación regioselectiva of alquinos aliphatic (1-octino and ciclohexilacetileno) and aromatic (fenilacetileno and 1-fenilpropino) with aromatic amines (2.6 - dimetilanilina and 2,6-diisopropilanilina) and aliphatic (tert-butilamina, dodecilamina and cyclohexylamine). The nature Markovnikov or anti-Markovnikov delos outputs depends on the nature aliphatic or aromatic both the alquino as the amine. The reactions of alquinos aliphatic aromatic amines give the products Markovnikov with regioselectividades of 100%, whereas with tert-butilamina and dodecilamina obtained derivatives anti-Markovnikov, also regioselectividades of 100%. The reactions of these alquinos with cyclohexylamine lead to mixtures of both products. The hidroaminaciones the aquinos aromatic lead only to products of addition anti-Markovnikov regardless of the type of amaina used. When comparing the results of all precursors studied shows that the efficiency of such systems increases under decreases the affinity group giver of ligand ciclopentadienilo indenilo towards titanium atom, ie the sequence Nme2 lower OMe -PPh2. In addition, since the complex amido-imido ((2,6-iPr2C6H3) NH) CpXTi (N = (2,6-iPr2C6H3)) (CpX = CpN, CpP) have proven to be completely inactive for the reactions of hidroaminación with 2 , 6-diisopropilanilina, this sequence suggests that during catalysis group giver is not coordinated the titanium atom. The role of the side chains funcionalizadas seems to be to prevent the formation of inactive species because of its demand for space. Accordingly, the precursors indenilo are so re-8 gioselec 419 tive as ciclopentadienilo for hidroaminación intermolecular of alquinos However, in terms of yields reaction, the precursor indenilo are more efficient than the species ciclopentadienilo for reactions using substrates less bulky, while the complex ciclopentadienilo are more efficient substrates for the reactions with more requirements estérico.

Author: DIAZ ALVAREZ ALBA ESTRELLA.
Year: 2006.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUIMICA.
Place of preparation: FACULTAD DE QUIMICA.

Summary: Chapter 1 describes the synthesis of new complexes of chiral ruthenium (II) containing ligands iminofosforano-fosfina type or. The first is obtained by monoiminación selective of the difosfina and subsequent coordination to a metal center. In contrast, recent generated complejando the same difosfina a fragment areno-rutenio, followed by a process of iminación. This will have prepared the complex regioisoméricos and (R = P (= O) (OPh) 2, p-C6F4CN). Depending on the rest R, treatment with salt originates silver compounds and mononuclear or species dinucleares and in which the ligand iminofosforano-fosfina serving as a bridge between the two metal centers. Moreover, it has studied the coordination of a tricyclic imino-fosfina chiral ligand fragments (? 6-areno) -rutenio (II) was observed in all cases processes totally diastereoselectivos. The optically pure synthesized derivatives have been used as precatalizadores in reactions Diels-Alder showing to be active, although the estereoselectividad induced low. The second chapter deals with the synthesis of complexes containing the ligand P (NMeNCH2) 3 (THPA) water-soluble. Thus, their coordination to a fragment areno-rutenio (II) or [MCl (COD)] (M = Go, Rh) leads to the formation of water soluble derivatives. The selective methylation of one of the nitrogen head of the THPA leads bridge to the formation of the complex fosfino-amonio. Derivatives obtained have proved efficient in the isomerization catalyst alcohols alílicos to form compounds carbonílicos for both organic and aqueous in the middle. Moreover, they are able to promote cicloisomerización (Z) -eninoles water to generate furans. The third chapter focuses on the preparation of complex dinucleares of ruthenium (II), rhodium and iridium (I) (I) with the difosfina P (NMeNMe) 3P (THDP) serving as a bridge linking. These derivatives have been used successfully as precatalizadores processes type Kharasch in aqueous medium. Thus, the addition of bromotriclorometano to olefins generates polihaloalcanos.

Author: SORIANO DOTOR MARIA LAURA.
Year: 2006.
University: CASTILLA-LA MANCHA [www.uclm.es].
Place of defense: FACULTAD DE CIENCIAS QUMICAS DE CIUDAD REAL.
Place of preparation: FACULTAD DE CIENCIAS QUIMICAS DE CIUDAD REAL.

Summary: The Supramolecular Chemistry is one of the most booming fields of chemistry and contemporary was defined in 1978 by Jean-Marie Lehn as "chemistry of molecular assemblies and of the intermolecular bond." Among the most popular goals of the Supramolecular Chemistry is the preparation of molecules receiving (host) specific for a limited number of substrates. The ligands bispirazolilazinas synthesized derivatives are quinoxaline, pirazina and piridazina, and presented four nitrogen atoms suitable for metal coordination centers. The design of these ligands is related to the existence of heterocyclic ring of wealth electronic variable, which will promote the presence of supramolecular interactions in the compounds prepared. These ligands have been chosen for our work because of its potential application in the development of building blocks for the propagation of their coordination resulting in derivatives polynuclear variable size. The principle of propagation in coordinating part of the simple fact that the coordination of these ligands to a single center metal leads to an entity in which there are vacancies coordinativas in central cash and an ability to coordinating the ligand. Both facts can not autocompensarse in-house construction unit, but by autoensamblado more of these units leading to polynuclear compounds. To this end have been carried out reactions of these ligands and metal salts of Cu (I), Ag (I), Co (II), Ni (II) and Cu (II) with a view to designing species metalopolímeros and metalociclofanos both dinucleares type (M2L2) as tetranucleares (M4L4) type grid [2x2] with different characteristics depending on the type of ligand, the geometry of the metallic center, the capacity coordinativa of anions in the presence of other molecules dadoras and conditions of reaction. In these derivatives were found multiple non covalent interactions that have been studied by X-ray diffraction studies of nuclear magnetic resonance (through experiments HOESY and DOSY). In a slightly different context, the use of derivatives 2,4-diamino-6-R-1 ,3,5-triazina allows the formation of supramolecular suspending different dimension (1D, 2D and 3D) in the presence of glutarimida and center metal Ag (I) and Cu (I), thanks to the use of hydrogen bond with amino groups of pairs of electronic nitrogen ring triazine neighbors. It noted the great versatility in geometry hit by the silver ion derivatives obtained with this center cash, while rates for coordinating 2, 3, 4, 5 and 6, the latter being an index of coordination unusual for the silver. Have also been prepared complexes of Ru (II) with some of these ligands bispirazolilazina to study its capacity as catalysts in hydrogenation processes for transfer of ketones. The process of hydrogenation of acetophenone and benzophenone presents a moderate and catalytic activity is influenced by the characteristics of the ligand, and the type of areno used.