ORGANOMETALIC COMPOUNDS

Author: PÉREZ CORTÉS YOLANDA.
Year: 2003.
University: REY JUAN CARLOS [www.urjc.es].
Place of defense: CIENCIAS EXPERIMENTALES Y TECNOLOGÍA.
Place of preparation: UNIVERSIDAD REY JUAN CARLOS.

Summary: 1-It has developed a family of complex alcóxido titanium (IV) with bulky ligands of estequiometría [Ti (OiPr) 4-n (OR) n] n = 1,2,4 (1-15). The most suitable method for the synthesis of these complexes is derived from l [Ti (OiPr) 4] do react with the corresponding quantity of alcohol. According to the spectroscopic data it is proposed that the complex of the type [(Ti (OiPr) 4-n (OR) n) 2] / 1-10) where n = 1.2, are dimers, where the two centers titanium are puenteados by ligands isopropóxido and titanium atom presents a distorted environment bipirámide trigonal. Instead complexes type [ti (OR) 4] 11-15, it is proposed that they are monomers, both in the solid state as dissolution, presenting a tetrahedral structure. 2-complexes alcóxido 7,8,9 and 10 were tested as catalysts enprocesos of epoxidación asymmetric alcohol cinámico, studying the influence of reaction time catalyst / substrate. The best results were obtained when it was used complex 8, reaching a surplus enantiomérico of 64%, for a catalyst / substrate (1 / 1) and a reaction time of 12 hours. 3, - have been synthesized complexes of titanium (IV) with ligands alcóxido attendants from derivative [Ti (O1Pr) 4], forming complexes mono, di and trinucleares, as the complex [(Ti (OiPr) 3) (O2C10H11) ] (16) [(Ti (OiPr) 3) 2 (O2C6H6N2)] (19) and [(Ti (OiPr) 3) 3 (O3C3N3)] (20), respectively. 4, have been prepared complexes minociclopentadienilo alcóxido dichloro titanium (IV) from derivative [TiCpCl3] do react with a corresponding equivalent of alcohol in the presence of NEt3. The study of X-ray diffraction of a monocristal the compound 27 and 28 shows that in both cases it is a mononuclear structure, where the titanium atom is bonded to a group ciclopentadienilo, in coordination n5, two atoms chlorine and the oxygen atom in the group alcóxido. The titanium atom is ready pseudo-tetraédrica. 5 - The reaction of three equivalents [TiCp MeCl3] with the equivalent of acid cianúrico, in the presence of NEt3 leads to the isolation of the complex trinuclear [(TiCp I Cl2) 3 (O3C3N3)] 29. According to the spectroscopic data of this complex, as well as the bibliographic data, we can propose a structure trinuclear, where are the three centers titanium enalzados the core of triazine. Therefore, the molecule exists in an axis of symmetry C3, perpendicular to the plane formed by the ligand triazine, and three axes C2, which contain a nitrogen atom and a group in position for replacement of triazine ring. 6 - The reaction of two equivalents of [TiCp I Cl3] with the equivalent of 2,5-dihidroxi-1 ,4-benzoquinona in the presence of NEt3 leads to the formation of the complex [(TiCpMe4Cl2) 2 (O4C6H2)] 30 next to the complex [(TiCpMe4Cl2) 2O] 31 as a result of hydrolysis, 30. Based on the spectroscopic data is proposed for the complex 30 structure dinuclear where every oxygen atom of the carbonyl groups of lignado benzoquinone is coordinated to a titanium atom, through a link dativo. The etudi of X-ray diffraction of a monocristal-31 confirms that this is a structure dinuclear where each titanium atom is linked to a group tetrametilciclopentadienilo, in coordination n5, two chlorine atoms and an oxygen atom, which keeps enalzados the two metal centers. The rings cilopentadienilo are available in anti-state solid. 7 - The reaction of comproporcionación between t etralcóxidos titanium 11.14 and 15 previously synthesized and in THF adduct of titanium tetrachloride, leading to the formation of the complex [TiCl2 (Oadam) 2 (THF) 2] 32 (TiCl2 (Oment) 2 (THF) 2] 8 33 and [Ti 4bd Cl2 (Oborn) 2 (THF) 2] 34. with spectroscopic data is proposed for these complex structure monómera, where titanium presents geometry octaédrica. 8 - The reaction among derivatives dialcóxidodiisopropóxido 7 and 8, previously synthesized and acetyl chloride, provides the complex [TiCl2 (ODAGP) 2] 35 and [TiCl2 (ODAGF) 2] 36, according to the spectroscopic data is proposed those present complex structure monómera, where titanium has tetrahedral environment.

Author: GARCÍA GARRIDO SERGIO EMILIO.
Year: 2004.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: Derivatives monocarbonilo [RuZ (n3-2-C3H4R) (P) (P ^ P)] (R = H, I, X = Cl, Br, P ^ P = dppf, dippf) experienced the loss of fragment n3-alilo in the presence of hydrogen halides HX generating species dinucleares [(RuX (uX) (XO) (P ^ P)) 2]. Similarly, a derivative (alilo) [Ru (n3 -2-C3H4Me) 2 (dppf)] reacts with hydrogen halides HX, in the presence of isocianuros, generating the complex trans, cis, cis- [RuX2 (NBC) 2 (dppf)] (X = Cl, Br, R = Bz, C, tBu, 2,6-C6H3Me2, (S )-(-)- C (H) MePh). In the presence of a base, both expecies [(RuX (uX) (P) (P ^ P)) 2] and trans, cis, cis- [RuX2 (CNR) 2 (dppf)] are efficient catalyst precursors reactions hydrogen transfer (TH) to ketones. The derivative trans, cis, cis- [RuCl2 (CN-2 ,6-C6H3Me2) 2 (dppf)] reacts with NaOEt resulting in the formation of the complex and dihidruro cis - mono, cis- [RuHCl (CN-2, 6-C6H3Me2) 2 (dppf)] and cis, cis, cis- [RuH2 (CN-2 ,6-C6H3Me2) 2 (dppf)], respectively. These species are active in hydride processes TH to ketones in the absence of bases. The abstraction of halide ligand in the complex monocarbonilo [RuX (n3-2-C3H4R) (P) (P ^ P)] by treatment with a silver salt leads to derviados of 16 electrons [Ru (n3 -2 - C3H4R) (P) (P ^ P)] [SbF6]. The complex [ru (n3 -2C3H4Me) (CO) (dppf)] [SbF6] is a precursor to efficient catalytic reactions replacement propargílica, as well as the isomerization of alcohols propargílicos compounds carbonílicos alpha beta-insaturados. In the presence of a hydrogen halide, the complex bis (alilo) [Ru (n3-2-C3H4Me) 2 (dppf)] reacts with alcohol propargílicos forming derivatives alquenil-carbino fac [RuX3 (= CC (H) = CR2 ) (dppf)] (X = Cl, Br, R = Ph, iPr, CR2 = C13H8). These carbinos react with a salt silver generating species alenilideno dinucleares [(RuX (uX) (= C = C = CR2) (dppf)) 2] (X = Cl, Br, R = Ph, CR2 = C13H8). The complex bis (alilo) ruthenium (IV) [RuCl2 (n3: n2: n3-C12H1)] (C12H18 = dodeca-2 ,6,10-trien1 ,12-diilo) and [(RuCl (u-Cl) ( n3: n3-C10H16)) 2] (C10H16 = 2,7-dimetilocta-2 ,6-dien-1 ,8-diilo) are precursors for highly efficient catalytic isomerization processes alcohols alílicos its related compounds carbonílicos both um half as organic water.

Author: SAEZ PÉREZ DAVID.
Year: 2004.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: In the work done has been synthesized different complexes dinucleares of Mo and W with ligands fosfuro and fosfinideno bridge and orders liaison metal-metal formally vary between one and three. These species are generated in reactions descarbonilación, oxidation and protonación and most have a high chemical activity in very mild reaction conditions. Among the chemical species whose behavior is remarkable is the radical [W2Cp2 (u-PPh2) 2 (CO) 2] + (19) and complexes with ligands fosfinideno: [Mo2Cp2 (u-PMes *) (CO) 4] (29 ), [Mo2Cp2 (u-PMes *) (u-CO) 2] (32) [Mo2Cp2 (u-k1: k1, n6 -PMmes *) (CO) 2] (33). The latter have proven to be of great versatility of behavior with respect to different substrates of organic and inorganic nature, occur in the course of the reaction activations links CH, PC, PH, SH, XX, GM, etc.. As well as training new links PCs, CH, DC. In addition, the presence of the aromatic ring Month * in the ligand fosfinideno enables him to act as a giver of 10 electrons, as in the species 33, where the ring is coordinated n6, and as a giver of 8 electrons sitaución that produced in other species sintetizads, as in the complex [Mo2Cp2 (u-k1: k1, n4-PMmes *) (CO (2] (51) and [CuMo2 (Cl) Cp2 (u-k1: k1; k1, n4 - PMes *) (CO) 3] (58). These results are particularly relevant because there was no precedent in the literature of this type of structure or behavior of chemical substrates dinucleares with ligands fosfinideno.

Author: FERNÁNDEZ GARCIA PABLO.
Year: 2004.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: In this Doctoral Thesis begins by describing the synthesis and characterization of new ligands derived from quinililciclopentadienilo and complexes of chromium (III) derived from them. From ciclopentadionas develops a new synthetic route for obtaining ligands with a group quinililo, which allows the introduction of a wide range of substituents on the ring ciclopentadienilo. Following is a study of the reactivity of the complex, in order to investigate the formation of active catalysts for the polymerization of ethylene. We report the spectroscopic analysis of these derivatives paramagnetic in depth by EPS and NMR. The interpretation partial displacement paramagnetic of 1H-RMn is achieved by comparison with reference spectra and by predicting the local spin density. However, it is difficult to a total allocation of signals observed due to the complexity of the systems. Because of these, DFT calculations were carried out to complete the assignment and to confirm previous results. We concluded that this approach would effectively identify the molecular structures of paramagnetic complexes in solution. Finally, we discuss the features of several complexes in the catalysis of reactions of polymerization of ethylene and copolymerization of etileno-1-hexeno. The catalysts presented here with a high activity and are stable at high temperatures. Both the activity of the catalysts as the properties of polymers produced can be changed by adding different substituents. In addition, the complex of chromium (III) derived from quinolilciclopentadienilo to broaden the range of polymers produced.

Author: PÉREZ MÉNDEZ SONIA.
Year: 2004.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: DPTO. DE QUÍMICA INORGÁNICA, FACULTAD DE QUÍMICA UNIVERSIDAD DE BARCELONA.

Summary: We have prepared and characterized the new Schiff bases of general formula [(n5 -C5H5) (Fe (n5 -C5H4) - C (H) = N-R2)] (with R2 = (CH2) 3-NMe2, C6H4- 2-Sme, C6H4-2-OH, (Sc) CH (Me) -CH2OH and (Sc) CH (CHMe2) -CH2OH) or [(2,4,6 - (R4) 3-C6H2) - C (H) = N-R2] (R4 = H R2 = C6H4-2-SMe or C6H4-2-OH and R4 = Me and R2 = C6H4-2-SMe) containing a heteroátomo additional (Namínico, SuO) the substituyente R2 and oxazina 2-ferrocenil-2 ,4-dihidro-1H-3 ,1-benzoxazina that dissolution coexists with the way imina [(Fe (n5-C5H5) (n5 -C5H4) - C (H) = N - (C6H4-2-CH2O))] through a balance tauromérico. The study of the reactivity of the new ligands face complex palladium (II) and platinum (II) under different experimental conditions has helped isolate and characterize coordination compounds where imina acting as a group (N) (N, N '), (N, S) or (N, O) giver and palada- or platinaciclos in which the ligand presents a way of coordination (C, N), (CN, N, N'), (C, N, S) (C, N, O) or (C, N, O) 2. The reactions of compounds ciclometalados with trifenilfosfina have allowed deduce that the lability of the link (M, E) (E = Namínico, SuO) increases as the sequence (C, N, O) -2 lower (C, N, S) minor (C, N, O) lower (C, N, N ') and in no case is the opening of metalociclo indicating that the link (M-Nimínico) presents a low lability. It has demonstrated the usefulness of some of the products prepared in summary organometálica and in the process catalytic alkylation alílica.

Author: GRABULOSA RODRÍGUEZ ARNALD.
Year: 2004.
University: BARCELONA [www.ub.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAT DE QUÍMICA.

Summary: The thesis deals with the use of catalytic asymmetric ligands phosphorus chiral -mono and bidentados- with atoms of phosphorus estereogénicos. The first part discusses the preparation of optically pure form ligands. The method is developed by Jugé, based on the use boranos how protective group of products phosphorus and ephedrine how chiral auxiliary. From an intermediate cyclic ephedrine, which atómo phosphorus is already resolved, two substitutions nucleofílicas providing fosfino-borano desired, to be treated with morpholine generates fosfofina free. In short, have been prepared and characterized families of fosfinas monodentadas enantioméricamente pure and estéricamente congested, as the general formula is in most cases (S) -PPhRR ', R = 1-naftilo, 9-fenantrilo, 1-pirenilo and 2-bifenilo R '= Me, iPr, -CH2SiMe3 and -CH2SiPh3. There have also been prepared difosfinas with a jumper -CH2CH2- or -CH2Si (Me2) CH2- between the two phosphorus atoms of optically pure form. In the second part of the thesis were used ligands phosphorus monodentados to prepare complex alílicos of general formula of palladium [Pd (alilo) Cl (P)], where P = ligand phosphide monodentado. The complexes have been characterized in detail (in solid and solution) and have been analyzed and streamlined different isomer presented and its mechanisms. Some of these complexes have been used as precursors in the reaction of hidrovinilación of styrene and derivatives, obtaining an excellent selectivity for 3-fenil-1-buteno in most cases (less 95%) and a enantioselectividad moderate (40% ee ) in some cases. There have also been prepared complexes alílicos cationic type of palladium [Pd (2-metilalilo) DB] PF6, where DB = two ligands foforados monodentados P-estereogénicos or difosfina P-estereogénica. After thorough characterization of these complexes have been used as precursors in the catalytic action of re alkylation alílica acetate 1,3-difenilalilo and acetate d ecinamilo under the usual conditions. In reaction to the first substrate, have yielded good activities and excesses enantioméricos of up to 74%, while the second substrate have been obtained also good activities, supported by good regioselectividades favoring linear isomer. Finally, the ligands phosphorus monodentados have also been used to prepare ruthenium complexes of the type [RuCl2 (p-cimeno) P], which have been characterized and used in ciclopropanación of styrene and alfa-metilestireno with diazoacetato ethyl and also the transfer of hydrogen from the acetophenone with isopropanol. In ciclopropanación, have yielded low or moderate activity, regioselectividades cis / trans and enantioselectividades moderate (up to 69% ee), while in the transfer of hydrogen has been obtained good activities but enantioselectividades low (45% ee, as maximum).

Author: Ares Morandeira Raquel.
Year: 2004.
University: A CORUÑA [www.udc.es].
Place of defense: Facultad de Ciencias.
Place of preparation: Facultad de Ciencias.

Summary: The work deals with the study of new compounds ciclometalados of palladium, which are of considerable interest because of the large number of applications submitted in the fields of organic synthesis, photochemistry, homogeneous catalysis, optical resolution, as metalomesógenos and as anti-tumor agents. First, it deals with the synthesis and characterization of a series of complex ciclometalados with Schiff base ligands derived from tereftaldehído, isoftaldehído and 3, 4-dimetoxivenzaldehído. As one of the most important aspects of the chemistry of compounds ciclometalados is studying its reactivity, then were carried out reactions of complex ciclometalados previously synthesized with different ligands: difosinas tertiary, differentiated primarily on the length and the nature of the chains of union between the two phosphorus atoms. Subsequently, has been extended to study the ligands homodifuncionales, rarer that difosfinas in the literature concerning the complex ciclometalados specifically diarsinas and diamminas. In the latter part has also studied the reactivity of the complex ciclometalados front of a wide variety of ligands bidentados heterofuncionales [Q, N), (P, As) and (P) O, and finally, ligands tridentados (P N, P), (P, N, N) and (Q, N, O). The complex thus prepared can be helpful in catalysis due to the multifunctional nature of ligands semilábiles employees, given by the combination in the same ligand of an atom together with a soft disk, which gives electronic asymmetry.

Author: AMOEDO PEREIRA ADRIANA.
Year: 2004.
University: SANTIAGO DE COMPOSTELA [www.usc.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUIMICA.

Summary: This work was raised in the context of ongoing research on reactions ciclometalación of ligands potentially bidentados [C, N], Schiff bases and tridentados [C, N, S] tiosemicarbazonas. For this study were used the following ligands. I) On the one hand, there were reacting the corresponding aldehydes and ketones with tiosemicarbazidas corresponding to the appropriate proportion to lead alos ligands tiosemicarbazona. II) In addition, the corresponding aldehydes were reacting with different amines to give rise to the Schiff base ligands. Later, it proceeded to the synthesis of compounds ciclometalados through reaction of these ligands with palladium salts, and then compounds ciclometalados resulting, once characterized, were reacting monofosfinas tertiary and various difosfinas obtained depending on the case, mononuclear compound with ligands monofosfina, disosfina chelate and difosfina terminal, and compounds dinucleares with ligands difosfina bridge between two metal centers. All compounds obtained have been characterized by the following techniques: elemental analysis (C, N, HyS), infrared spectroscopy, nuclear magnetic resonance spectroscopy of 1H and 31P- (1H) and structural analysis by X-ray diffraction

Author: MADRIGAL GUTIERREZ CESAR ALBERTO.
Year: 2004.
University: OVIEDO [www.uniovi.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: The complex pentacoordinado [RuCl2 (PPh3) (FcPN)] reacts with phosphine ligands and fosfito to generate derivatives hexacoordinados [RuCl2 (PR3) 2 (FcPN)] (PR3 = PMe3, PMe2Ph, P (Ome) 3). Similarly, the reaction to fosfinas bidentadas leads to the formation of complexes [RuCl2 (DB) (FcPN)] (DB = dppe). The change under the reaction conditions used to obtain different diastereomers and have studied the processes of isomerization fac-mer that pass through the formation of an intermediate pentacoordinado cationic that for the complex with ligand dppm has been asylee as salt hexafluorofosfato [ RuC1 (dppm) (FcPN)] [PF6]. The reaction of [RuCl2 (PPh3) (FcPN)] carbon monoxide leads to carbonyl species [RuCl2 (CO) L (FcPN)] (L = PPh3, CO), which are capable of decoupling a ligand L obtaining the complex dinulcear [(RuCl (u-C1) (CO) (FcPN)) 2]. The complex [RuCl2 (CO) (PPh3) (FcPN)] reactions experienced replacement PPh3 by ligands mono or bidentados generating especis [RuCl2 (CO) L (FcPN)] (L = PMe3, PMe2Ph, Py) and [ RuCl (CO) (dppm) (FcPN)] (FcPN)] [PF6]. We have developed efficient synthetic routes to the complex semi-sándwich [RuCl (n5 -C9H7) (FcPN)], [Ru (n5-C9H7) (PPh3) (FcPN)] [PF6] and [ruCl (n6-areno) FcPN)] [PF6] (n6-areno = p-cimeno; 1,2,3,4-tetrametilbenceno) by reaction FcPN with [RuCl (n5 -C9H7) (cod)], [RuCl (n5 -C9H7) ( PPh3) 2] and [RuCl2 (n6-areno)] 2, respectively. Reactions metátesis of chloride ligands in these derivatives have helped synthesize complex [RuH (n6-p-cimeno) (FcPN)] [PF6] and [Ru (N3) (n6-p-cimeno) (FcPN)] [PF6] . The reaction of the complex [RuCl (n5 -C6H7) (FcPN)] with alquinos terminals and alcohols propargílicos allows synthesize complex alquinilo [Ru (n1-C = CC6H4R-4) (n5-C9H7) (FcPN)] (R = H Me), alenilideno [Ru (n5 -C9H7) (C = C = CPh2) (FcPN)] [PF6] and I toxialquenilcarbeno [Ru (n5-C9H7) (= C (Ome) C (H) = CHPh) (FcPN )] [PF6]. Both complexes octaédricos [RuCl2L2 (FCPN)] (L = PMe3, PMePh, P (Ome) 3) as the complex semi-sándwich [RuCl (n5 -C9H7) (FcPN)], [Ru (n5 -C9H7) (PPh3 ) (FcPN)] [PF6] and [RuCl (n6-areno) (FcPN)] [PF6] are efficient catalysts for hydrogen transfer processes to reduce ketones. Some of these catalysts are among the most efficient and selective described in the literature anantioselectividades up 95%.

Author: BARRIO SENA MARÍA DEL PILAR.
Year: 2004.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: This report describes reactions activation of carbon links (sp2) -hidrógeno ketones, olefins, aldehydes and aldiminas, carbon (sp2) -flúor ketone and carbon (sp3) -hidrógeno of cicloalquilcetonas promoted by the complex hexahidrurobis (triisopropilfosfina) osmium (VI). Also, competitive processes are studied activation of CH and FC links, using non-fluorinated aromatic ketones, perfluoradas and partially fluorinated, and are carried out catalytic reactions coupling carbono-oxígeno of aldehydes (reaction Tishchenko). The resulting products are derived trihidruro of osmium IV can be transformed into elongated dihydrogen complex. In such species, a hydrogen atom interacts with the electrostatic so ligand L in cis position. Derivatives dihydrogen elongated react with alquinos terminals to complex links osmio-carbono of order 1, 2 and 3. Under certain conditions, the fragments can connect generating organic species with unusual structures, emphasizing the formation of the first isometalobenceno with structure 1,2,4-ciclohexatrieno.

Author: GARCÍA MONFORTE Ma. ANGELES.
Year: 2004.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: The objective of this work has been the systematic study of the behavior of ligands C6Cl5 and C6F5 with metals of the first series of transition. To do so, through the treatment of metallic substrates most appropriate in each case with LiC6X5, we have prepared the perhalofenil-derivados homolépticos all of them except for Mn. In the specific case of ligand C6Cl5 we obtained in all cases derivatives tetrasustituidos of general formula [M (C6Cl5) 4] qÓ (q = 0, 1 or 2). While the formula of pentaclorofenil-derivados thus obtained is independent of the state of oxidation and the electronic configuration of the metal center; the same is not true geometry of each compound [M (C6Cl5) 4] qÓ which is greatly dependent on this last factor. Thus, the geometry of the species tetrasustituidas configuration electronic d0, d1 and d2 is a tetrahedron elongated. The geometry of anion [CrIII (C6Cl5) 4] Ó, configuration electronic d3, can be described as a heavily distorted octahedron and the species electronic configuration between d4 and d8 is best described as square flat. With the group C6F5 not only geometry, but even estequiometría of species homolépticas depend on the configuration of the electronic cash center. When the electronic configuration of the metal is d1 and d2, obtained species pentacoordinadas formula [M (C6F5) 5] 2Ó and geometry bipirámide trigonal with a strong distortion that follows the opposite path to pseudorrotación Berry usual. The anion [CrIII (C6F5) 5] 2Ó, configuration electronic d3, but it is also pentacoordiando presents a geometry pyramid square base and the other electronic configurations (d4-d8) are obtained species tetracoordinadas [M (C6F5) 4 ] qÓ with tetrahedral geometry in the case of anion [Fe (C6F5) 4] 2Ó (d6) square and flat in others. The study reveals the existence of electrochemical processes electronic exchange for all compounds tetrasustituidos [M (C6X5) 4] qÓ, with the exception of Faith. In all cases we have been able to prepare and characterize other species involved in these redox processes. Compounds pentacoordinados [M (C6F5) 5] 2Ó, on the other hand, show no defined processes electronic exchange, which could be attributed on the one hand to their low stability in solution, and on the other to different estequiometría to be expected for both as for the species oxidized low.

Author: DIOSDADO CABRERA BEATRIZ EVANGELINA.
Year: 2004.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: In ete work reflected the synthesis and characterization of a large number of mononuclear platinum complexes with different ligands giving nitrogen. Some of these complex interactions Pt-H by presenting bridge hydrogen intra or inter-in solution and / or solid state. Interactions for bridge structural hydrogen have great relevance in some of the products obtained in the form supramolecular aggregates. To systematize the study of these interactions has designed a parameter, selecting the most important structural aspects of these interactions in solid state. This parameter has higher values for interactions Pt-H by bridge hydrogen stronger. The mononuclear complexes, with or without interactions Pt-H have been used in the synthesis of complex binucleares, some of which show links GM ', a dador-aceptor. It also describes the formation of aggregates binucleares from interactions by hydrogen bridge. Depending on the possibilities coordinativas some of the ligands are designed new routes for the synthesis of complex bi - or trinucleares without links GM reached in some cases, new ways of coordinating some of the ligands used.

Author: MARTÍN JULIÁN LUIS FRANCISCO.
Year: 2004.
University: ZARAGOZA [www.unizar.es].
Place of defense: FACULTAD DE CIENCIAS.
Place of preparation: FACULTAD DE CIENCIAS.

Summary: In the present paper has studied the reactivity of metal fragments of the group 10 who have one or two vacancies coordinativas with different unsaturated molecules (CO alquenos and arenos). This has led to a comparative study of the properties of the link M-ligando over Group 10. As metallic substrates with two vacancies coordinativas have been chosen fragments "M (C6F5) 2" (M = Ni, Pd and Pt), while coordination metal fragments with a single vacancy coordinativa has been carried out with the substrate neutral Pt of "Pt (C6F5) 2 (CO) and with metal fragments anionic [M (C6F5) - (M = Ni, Pd, Pt). The coordination of different types of olefins and arenos the fragment "Pt (C6F5) 2 (CO)" has allowed us to study the influence of different electronic effects estéricos and ligand in its link to the metal. In addition the synthesis of complex family [NBu4] [M (C6F5) 3 (-2-C2H4)] (M = Ni, Pd, Pt) allows to compare the different stability of the link M-etileno over the group. This, according to some recent theoretical calculations, it has been estimated that dramatically decreases in the order Pt> Pd> Ni. This paper has also tested the reactivity of the fragment "cis-Ni (C6F5) 2" with other ligands unsaturated monodentados (CO and CNtBu) various organic systems that bind to the metal through the electron density - (alquenos and arenos ). We have managed to synthesize the compound cis- [Ni (C6F5) 2 (CO) 2]. This complex is the first dicarbonil-derivado Ni (II) is known, and its synthesis has been an unprecedented series of dicarbonil-derivados for the three group metals 10. In conclusion, it has presented the reactivity of metal fragments acid group 10 with one two vacancies coordinativas versus unsaturated ligands, with different availability of electronic metal fragment on the basis of the global burden and the type of ligand. In cases that have been able to characterize compounds similar to the three metals can be seen that there is a direct relationship between the stability and order of the degree of retrodonación of electron density.

Author: RENDÓN MÁRQUEZ NURIA.
Year: 2005.
University: SEVILLA [www.us.es].
Place of defense: INSTITUTO DE INVESTIGACIONES QUÍMICAS, CSIC-UNIVERSIDAD DE SEVILLA, ISLA~DE LA CARTUJA.
Place of preparation: INSTITUTO DE INVESTIGACIONES QUÍMICAS.

Summary: The Doctoral Thesis, studies the reaction with various alquinos a complex Ir (I) 18 electrons containing the ligand TpMe2 (hidrotris (3,5-dimetilpirazolil) borate) coordinated through the three rings pirazolilo and a ligand 2.3-dimetilbutadieno. It is also studying the reactivity of the species obtained, especially its interaction with other molecules unsaturated. This compound 2,3-dimetilbutadieno reacts with a (trimetilsilil) with acetylene formation of a stable complex vinylidene. The process requires a reorganization of electronics ligand dieno and conseguiente increase in oxidation of the metal, +1 to 3 +. The protonacion that vinylidene acid trifluoracético produces a iribabeneno, probably through an intermediary cationic containing a ligand carbino. The reaction from the same precursor with different tolanos leads to the formation of derivatives alílicos related whose structures show incorporating an equivalent of alquilino to dieno original. The mechanism of formation of these species is proposed based on the study of the reactivity of one of these derivatives with NCMe. For its part, the reaction of the precursor and cited acetilendicarboxilato dimethyl (DMAD) comes with displacement of ligand dieno and formation of a iridaciclopentadieno or iridacicloheptatrieno, depending on the experimental conditions. Both represent intermediate commonly accepted in the process of ciclotrimerización of alquinos catalyzed by transition metals. The reaction of various metalacicloheptatrienos with different oxidizing agents allows selective oxidation, forming groups ceto into final products. The sobreoxidación of these species leads to derivatives metaloaromáticos (specifically an iridabenceno and iridanaftaleno) through a process of type Baeyer-Villilger. The reactivity of metalaciclopentadieno prepared opposite alquinos depends on the nature of these products and, as appropriate, entering the compound one or two equivalents of the same. In the reaction with 2-butino, one of the products obtained proves to be a derivative organometálico structure Bicycle [3.2.0] hepta-1 ,3,6-trieno, product represents the first example of this type of experimental compounds. With alquinos terminals, metalaciclopentadieno reacts so that incorporated two equivalents of them. As for the reaction of the aforementioned iridaciclopentadieno whose substituents are all groups CO2Me, propene or 1-buteno, is the coupling of the corresponding olefine with iridium complex, generating derivatives iridabenceno with a hydride ligand. It is postulated that these species are formed through alquilidenos Iridium resulting from the isomerization of alquenos coordinated to the metal center. The change in a group CO2Me by a hydrogen atom, in the position beta metalaciclopentadieno, produces a surprising change in reactivity off the olefins propene and 1-buteno. Thus, although there are also iridabencenos, now has a metal atom ligand methyl, which is a break of the CC olefine.

Author: Besora Bonet Maria.
Year: 2005.
University: AUTÓNOMA DE BARCELONA [www.uab.es].
Place of defense: Facultat de ciències.
Place of preparation: Autònoma de Barcelona.

Summary: This thesis presents the results found in the study of behavior classic links Sigma organometallic complexes. The investigation can be considered divided into two parts that are common in the study, computational techniques, transition metal hydrides in the formation of non-traditional species. The first set deals with the transfer protónica Transition metal hydrides, with the aim of characterizing the structure of reactants, intermediates and products protónica transfer mechanism, as well as its relative stability. We also have characterized the factors that control these reactions. In the second block has studied the formation of structures unusual "SiHR2", in order to characterize and understand the relative stabilities a small variety of stable isomers.

Author: TOUCEDA VARELA M. ÁNGELES.
Year: 2005.
University: SANTIAGO DE COMPOSTELA [www.usc.es].
Place of defense: FACULTAD DE FARMACIA.
Place of preparation: FACULTAD DE FARMACIA.

Summary: This paper deals with the study of the interaction of various metallic salts and organometallic with tiosemícarbazonas from a-and beta -cetoestéres and beta-cetoamidas and tiosemicarbazidas a-aciladas, as well as the ability to ciclación these lígandos in the presence of these metal salts . For this, we selected first metallic cations Group 14 (Sn (II), Pb (II) R2Sn (IV) and R2Pb (IVÂ "to test the ability of ciclación of these cations in the presence and absence of impediments estéricos and the electronic effects generated by clusters when joined to the metal Check compounds Sn (lI) and R2Sn (IV) have a low reactivity against these metal salts, since in no case was isolated complexes. however , Pb (lI) and R2Pb (IV) show a high reactivity with these ligands, isolated complexes pirazolonato (formed by ciclación of tiosemicarbazonas from f1-cetoésteres) tiosemicarbazonatos and triazine (formed by ciclación a tiosemicarbazona from one - cetoéster) Pb (lI) and adutos (1:1 or 1:2) with chloride difenilplomo with ligands tiosemicarbazona and a complex 2:1 or an adduct 1:2 with ligands tiosemicarbazida. acetate difenilplomo ( lV) allowed isolate a large number of compounds demonstrating the high reactivity of this metallic substrate with ras tiosemicarbazonas and tiosemicarbazidas. way, we could isolate and characterize compounds pirazolonato and tiosemicarbazonato of difenilplomo (lV), which were studied by elemental analysis and action spectroscopic yen some cases by X-ray diffraction, which revealed in the case of complex pirazolonato the monodesprotonación of ligand and coordination through the atoms SyN (3); And in the case of tiosemicarbazonatos coordination through the S atoms, NYO the ligand acting as tridentado. Emphasize that all these compounds may suffer processes protodesfenilación and reduction of Pb (lV) Pb (II), together with the ciclación of ligand tiosemicarbazona. also was isolated from these reactions this metallic substrate complex with ligand 1,3,4-triazol-5-tiona formed by ciclación a tiosemicarbazida a-acilada 1-fenilacetil-4-fenil-3-tiosemicarbazida). these reactions with the ligands tiosemicarbazida, besides are isolated complexes with ligands mono or bi-desprotonados well as bi compounds and trinucleares and complex Pb (lI) obtained in a process desfenilación and reduction. Where ligands tiosemicarbazona and tiosemicarbazida react with derivatives of palladium and platinum in molar ratio 1:2 (M: L) are formed tiosemicarbazonatos and / or pirazolonatos and study by X-ray diffraction indicates that the ligands are N, S-coordinados and field coordination of the metal is plano-cuadrada trans, more or less distorted. Some of these compounds Pd (II) and Pt (II) introduced in vitro, a very promising activity against cell lines resistant to cisplatin. How endpoint of this study was reacting M (OAc) 2 ( M = Zn and Cd) with tiosemicarbazonas derived from to - and B-cetoésteres and -cetoamidas isolated corresponding tiosemicarbazonatos (with -cetoestéres and -cetoamidas tiosemicarbazonas) or pirazolonatos (with a -cetoésteres tiosemicarbazonas). antiinflammatory activity in vivo any of the compounds pirazolonato Zn was tested using the test endema planting induced in rats by carrageenan observed that these compounds have no anti-inflammatory activity as opposed to what happens to the free ligands Pyrazolone that reduce inflammation around a 50% .

Author: CARRION LOZOYA PEDRO.
Year: 2005.
University: CASTILLA-LA MANCHA [www.uclm.es].
Place of defense: FACULTAD DE CIENCIAS QUÍMICAS (CIUDAD REAL).
Place of preparation: FACULTAD DE CIENCIAS QUÍMICAS (CIUDAD REAL).

Summary: One of the lines of our Research Group studied the synthesis and characterization of new metallocene complexes and their application in catalytic olefin polymerization, both in homogeneous conditions, as supported. This report has made a comparative study between the metallocene complex [Cp (CH2CH2CH2OSiMe)] CpZrCl2 (RY1), synthesized and characterized by Repsol-YPF, and metallocene without equivalent replacement in the ring, Cp2ZrCl2. The objective of this study is to see improvement provided by the introduction of replacement CH2CH2CH2OSiMe3 in a ring ciclopentadienilo for heterogeneización of metallocene and the catalytic polymerization of olefins in half heterogeneous. To that end, it has studied the model fixation metallocene on a common stand, the silica. This determination has been made by impregnating direct metallocene on the stand deshidroxilado without pretreatment, and others modified to a greater understanding of how fixing metallocene to the stand. In monitoring the reactions fixing metallocene activation and catalytic polymerization of ethylene have used the techniques of ultraviolet and infrared spectroscopy. It has also been studied in the same way, the way to get a heterogeneous catalyst for the polymerization of olefins, based on the complex RY1, that is as active as possible. This has been studied using other cocatalizadores and use another method of fixing catalysed by setting previously cocatalizador and subsequently metallocene. The report is divided into a section of bibliographic record, which introduces catalysis with metalocenos and describes the "state of art" of metallocene catalysts supported, from an academic point of view. Then there is a discussion of results, with a corresponding Experimental Procedure. Finally, it outlines the conclusions obtained from the study. This work is part of the investigation which is developed under a project funded by Repsol-YPF, entitled "Synthesis and Characterization of Metalocenos Supported." The reaction between complex Cp27rCl2 and silica SiO2 (773), average temperature, anchoring metallocene produced by reaction between groups silanol acids and bridges siloxano reagents to the surface, with links Zr-Cl. This process leads to links -oxo of species circonoceno with the surface. Moreover, the complex RY1, besides fixed the same way as the Cp27rCl2, also is set through the functional group O-SiMe3 present in the chain replacement of the ring, by reaction with groups siloxano reagents. This reactivity makes fixing more complex RY1 to the surface of silica that the complex Cp27rCl2. On the other hand, this chain will act as a spacer vertically, giving the metallocene supported a provision similar to the more complex situation in uniform, thus demonstrating a greater than the previous catalytic polymerization of ethylene. When the silica was amended with EtOSiMe3 or with (Me3Si) 2O, to create an area with a low concentration of groups SiMe3, the reaction occurs with metallocene probably eliminating ClSiMe3 and the formation of the same species -oxo. This route leads to a higher content of zirconium endured, a situation in contrast to the modified fused silica with organosilanos previously described. These species have a moderately high activity in the polymerization of ethylene after being activated with a low concentration of MAO. Higher grades sililación with (Me3Si) 2NH produce deactivation d 8 and the sup 940 erficie for the subsequent reaction anchor of metallocene to average temperatures. In this case, there were only low catalytic activities. The use of TIBA and B (C6F5) 3 for activation of the catalyst, replacing MAO, is not an effective technique, since in no case was obtained as a catalyst active. By contrast, the use borate anilinio [HNMe2Ph] + [B (C6F5) 4] - there is a heterogeneous catalyst in polymerization of ethylene active, but not exceed the activity shown when using MAO as cocatalizador. When Using another route immobilisation of metallocene setting previously MAO on the silica and subsequently metallocene, it is noted that there is a more active catalyst in polymerization of ethylene for both metalocenos. Here you can also see how the complex RY1 well supported shows an activity greater than the complex Cp27rCl2. For the preparation of supported catalyst for the polymerization reaction of ethylene, it is more convenient to use a reactor stirring blades, which does not destroy the particles of support, leading to some late polymer particles suitable because they have a morphology fairly steady . The heterogeneización of metallocene by impregnating not directly leads to a polymer regular and uniform size because probably, a worse distribution of the catalyst on the silica particles and by the possibility of presenting phenomena of "leaching" after being activated by MAO. This seems not presented in the case of catalyst supported on silica previously modified with MAO because the resulting polymer particles are replicas acceptable particles bracket.

Author: Gálvez López María Dolores.
Year: 2005.
University: MURCIA [www.um.es].
Place of defense: Facultad de Biología.
Place of preparation: Facultad de Química.

Summary: This thesis describes the synthesis and reactivity study structural platinum complexes with the ligand 3,4,5-trimetoxidinitrofenilo. It is structured into eight chapters as described below, and two appendices which is reflected in the work done in placements at York University on carbeno complex rhodium and use of the technique of polarization induced parahidrógeno (PHIP) under the supervision of Prof.. Robin N. Perutz and Dr.. Simon B. Duckett, respectively. At the end is a summary in English, according to the requirements for seeking the endorsement of European Doctorate. Chapter I is an introduction to the methods used in the preparation of orto-nitroaril metal complex in which the background known. Chapter II consists of three distinct parts. The first is an introduction to methods of synthesis of aril complex platinum (II). The second part begins exposure of the results and discussion. It describes the synthesis of complex diaryl platinum (II) cis-Q [Pt (k2-Ar) (k1-Ar) Cl] [Q = Ph3PCH2Ph (1), NMe4 (2); Ar = C6 (NO2 ) 2-2,6 - (OMe) 3] by transmetalación with [HgAr2] to Q2 [Pt2Cl6] or (NMe4) 2 [PtCl4]. The reactions of 2 with various reagents leads to the synthesis of cis-diaril complex. Have also been studied isomerization processes such complex, obtaining, in some cases, the corresponding trans-diaril derivatives. The third part deals with the synthesis and reactivity of monoaril complex platinum (II). The preparation of monoaril derivatives departure was carried out by two procedures: transmetalación from a diaryl complex platinum (II) to a salt of mercury and protonolisis. In Chapter III is a brief introduction on routes synthetic aril complex platinum (IV) and describes the synthesis of new complexes platinum (IV) by oxidation of some of the complex platinum (II) described PhICl2, reactivity and face various reagents. In Chapter IV, after a brief analysis of the known history, outlined the study the reactivity of some of the complexes synthesized platinum (II) salts in front of mercury (II) and the addition of oxidant [HgAr2] Complex platinum (0). These reactions result in different behaviors such as the formation of complexes with links Pt-Hg exchange between ligands centers metallic transmetalación a ligand arilo platinum to mercury and isomerization of the complex of platinum. In Chapter V discusses the characterization of the compounds synthesized primarily through studies of X-ray diffraction methods spectroscopic (NMR, IR). Also included are two paragraphs that refer to elemental analysis, molar conductivity and color of the complex. In Chapter VI reflects the experimental conditions for the synthesis of new complexes and their analytical and spectroscopic data. In Chapters VII and VIII are the findings and literature, respectively.

Author: LÓPEZ NICOLÁS ROSA MARÍA.
Year: 2005.
University: MURCIA [www.um.es].
Place of defense: FACULTAD DE BIOLOGÍA.
Place of preparation: FACULTAD DE QUIMICA. UNIVERSIDAD DE MURCIA.

Summary: THESIS ON THIS IS DESCRIBES THE PREPARATION OF OLIGOTIOÉTERES FROM YODUROS OF ARILO BY REACTIONS LINKAGE CS, FOLLOWING AN AMENDMENT OF METHOD OF SHOPFER. WITH THE PURPOSE OF FUNCIONALIZAR THESE TIOÉTERES BE LED OUT IN FIRST PLACE, THE OXIDACIÓN OF SOME OF THEM SULFÓXIDOS FOLLOWING DESCRIBED BY BARBIERI A METHOD AND PARTNERS, AND ACROSS THE PREPARATION OF ARIL COMPLEX OF PD (II) THROUGH THE ADDITION OXIDANTE OF BROMOARILTIOÉTERES ABOVE MENTIONED A SPECIES PALADIO (O). BELOW IS ESTUDIÓ THE REACTIVITY OF ARILCOMPLEJOS OF PD (II) THE FACE MOLÉCULAS INSATURADAS SUCH AS CO ISOCIANUROS Or ALQUINOS. FINALLY IS RECOGEN RESULTS ACHIEVED DURING A VISIT TO THREE MONTHS IN THE UNIVERSITY OF EXETER, ON THE GROUP OF DR. ROBIN BEDFORD, IN WHICH PREPARARON FOSFITOS CICLOPALADIADOS CONTAINING LIGANDOS CARBENO HETEROCÍCLICOS AND ESTUDIÓ ACTIVITY CATALÍTICA therefrom REACTIONS IN SUZUKI.

Author: ADRIO CASTIÑEIRA LUIS ANGEL.
Year: 2005.
University: SANTIAGO DE COMPOSTELA [www.usc.es].
Place of defense: FACULTAD DE QUÍMICA.
Place of preparation: FACULTAD DE QUÍMICA.

Summary: This work was raised as part of ongoing research on reactions ciclometalación of tiosenmicarbazonas as ligands potentially terdentados (C, N, S). For this study were used the following ligands tiosemicarbazona, synthesized by condensation of 2, 3, 4-trimetoxibenzaldehído 2, 4 and 2,5-dimetilbenzaldehído, 2-tiofencarboxialdehído and 2-acetiltiofeno and 2-acetiltiofeno, 3-tiofencarboxialdehído and 3-acetiltiofeno , 5-metil-2-tiofencarboxialdehído, N-metil-2-pirrolcarboxialdehído, 4-bromacetofenona, acids 3 and 4-acetilborónico and acid 3-and 4-formilborónico with corresponding tiosemicarbazidas. These ligands were made to react with salts Pd (II) in order to obtain the corresponding compounds ciclometalados. The salts used were as follows: tetracloropaladato potassium tetracloropaladato lithium, tetracloropaladato sodium acetate and palladium. Once synthesized, these compounds were reacting difosinas tertiary (dppm, dppe, dppp, dppb) and trifenilsofina. The compounds obtained have been characterized by the following techniques: elemental analysis (C, N, HyS), infrared spectroscopy, nuclear magnetic resonance spectroscopy of 1H, 31P- (1H) and structural analysis by X-ray diffraction In a second part of the thesis, we studied the catalytic activity of some of the complexes synthesized in the reaction of Suzuki-Miyaura. Based on the results obtained, a ranking that relates the structure of the complex with his activity as a catalyst.