Amine bis(phenolate) ligands synthesis can be easily prepared by the reaction of a substituted 2-(bromomethyl)phenol, a substituted phenol, potassium carbonate, triethylamine and the appropriate amine to form the desired compounds in high yields and purities. A series of amine bis(phenolate) ligand precursors with group 4 metals and aluminum complexes have been prepared, characterized by single-crystal X-ray diffraction, and tested for ring opening polymerisation of £`-caprolactone. Group 4 metals complexes which are shown to be active catalysts for the ROP of £`-caprolactone with excellent conversions and polydispersities. All aluminum compounds as four-coordinate aluminum methyl complexes show excellent catalytic activity toward the ring opening polymerization of £`-caprolactone in the presence of benzyl alcohol. And amine bis(phenolate)s ligand ([tert-ButylONO]2-) bond cleavage with zirconium and hafnium complexes that have been prepared, characterized by single-crystal X-ray diffraction. Another zirconium complexes of dianionic amine bis(phenolate) ligands have been synthesized, their X-ray structures solved, and their activity as 1-hexene polymerization catalysts study. Upon treatment with B(C6F5)3, a series of pentacoordinate [ONO]Zr(CH2Ph)2 complex, having no extra donor group, shows only poor activity as a polymerization catalyst. Final reaction of diamine-bis(phenol) ligands containing a mixture of [i-PropylONO]Ti(OiPr)2 in dry THF under RT without exclusion of air and moisture gives {[i-PropylONO]TiO}3 (characterised by X-ray crystallography) is hydrolysed with H2O.

La complexation des ions Th(IV), U(VI), Am(III) et Pu(IV) avec le ligand hydrophile SO3-Ph-BTP4- et des ions Th(IV) et Pu(IV) avec le ligand hydrophile SO3-Ph-BTBP4– a été étudiée. Ces nouveaux ligands ont été proposés dans le cadre du recyclage des combustibles nucléaires usés, pour la séparation sélective d’actinides(III) par rapport aux lanthanides(III) et aux produits de fission. L’objectif de ce travail était d’étudier la capacité de ces ligands à complexer les actinides de degré supérieur, soit IV et VI. Après des essais infructueux par spectroscopie directe, la méthode appliquée pour atteindre cet objectif est une étude par extraction liquide-liquide. Le système d'extraction est composé de deux ligands chélatants qui sont en compétition pour complexer les ions actinides: l’extractant tétraoctyldiglycolamide (TODGA), molécule neutre, lipophile, donneur oxygéné tridenté et le complexant anionique hydrophile tridenté (ou tétradenté) SO3-Ph-BT(B)P4–. La méthode consiste à mesurer l’évolution de l’extraction du cation par le TODGA (DM) lors de l’ajout de quantité croissante de complexant en phase aqueuse, tout en fixant une force ionique constante en phase aqueuse. Un modèle mathématique est établi en prenant en compte les équilibres d’extraction et de complexation, il permet d’évaluer la stœchiométrie des complexes formés et leurs constantes de stabilité relatives. Les expériences réalisées ont permis de conclure à la présence des complexes An:SO3-Ph-BTP4– 1:1 et 1:2 pour tous les actinides testés et du complexe 1:1 pour An(IV):SO3-Ph-BTBP4–.Deux séries de constantes conditionnelles de stabilité de ces complexes ont été déterminées dans nos expériences: des constantes de stabilité conditionnelles, αL,i, valables pour une solution 1 M en nitrate et faciles à évaluer et des constantes ßL,i, considérant de manière explicite la complexation des cations par les nitrates, toujours pour une force ionique I = 1 M. En considérant les constantes conditionnelles de stabilité ßL,i, des actinides pour les ligands SO3-Ph-BTP4- et SO3-Ph-BTBP4-, l'ordre suivant est observé: UO22+ < Am3+ < Th4+ < Pu(IV), conformément à l’augmentation du potentiel ionique z/r2, où z est la charge formelle et r est le rayon de l'ion métallique. L'analyse des valeurs ßL,i suggère que les effets électrostatiques jouent un rôle plus important dans la formation des complexes entre les ligands azotés polydentés et les ions actinide.Pour les complexes de Am3+ avec le ligand SO3-Ph-BTP4– tridenté, si on compare nos résultats avec l’étude menée par TRLFS (fluorescence laser à résolution temporelle) pour des complexes analogues de Cm3+, les constantes de stabilité de stoechiométrie 1:1 et 1:2, déterminées par extraction liquide-liquide sont plus faibles. En outre, la stœchiométrie 1:3 décrite pour Cm3+ n'a pas été détectée dans notre étude. Les constantes de stabilité des complexes SO3-Ph-BTP et SO3-Ph-BTBP avec les actinides(IV) n'ont pas été rapportées dans la littérature. Néanmoins les complexes supérieurs n’ont pas été observés: 1:3 avec le ligand tridenté SO3-Ph-BTP4– et 1:2 avec le ligand tétradenté SO3-Ph-BTBP4–. Ces observations surprenantes à priori peuvent provenir du traitement mathématique simplifié des équilibres chimiques et nécessiteraient des vérifications supplémentaires par des techniques permettant d’identifier les complexes en solution. Cependant, les données de partage obtenues ont permis de proposer des constantes de stabilité conditionnelles qui peuvent être exploitées pour modéliser le comportement des actinides (III), (IV) et (VI) dans un procédé de séparation. / The complexation of Th(IV), U(VI), Pu(IV) and Am(III) with the hydrophilic ligand SO3-Ph-BTP4–, and of Th(IV) and Pu(IV) with the hydrophilic SO3-Ph-BTBP4– ligand was studied. These new hydrophilic aromatic poly-N-dentate ligands are proposed, in the frame of recycling spent nuclear fuel, for a selective separation of actinides(III) from lanthanides(III) and from other fission products. The aim of this work was to compare the ability of the actinide ions to coordinate these N-dentate molecules. After some disappointing tests with classical spectroscopies, the method of liquid-liquid (solvent) extraction was applied to reach this goal. The extraction system consisted of two chelating ligands that competed for the actinide ions: a lipophilic tri-O-dentate neutral molecule of dioctylamide (TODGA) and a hydrophilic tri(or tetra)-N-dentate anion SO3-Ph-BT(B)P4–. The simple model we applied, well known in literature, considered chemical equilibria resulting in accumulation of the metal complexes with the lipophilic ligand in the organic phase, and those with the hydrophilic ligand – in the aqueous phase. With increasing concentration of the hydrophilic ligand (the concentration of the lipophilic ligand being constant) the equilibrium shifted towards the complexes with the hydrophilic ligand, and the distribution ratio of the metal decreased.The results have been interpreted in terms of the formation of 1:1 and 1:2 actinide complexes with tridentate SO3-Ph-BTP4– and only single 1:1 An(IV) complexes with tetradentate SO3-Ph-BTBP4– ligands in the two-phase systems studied. Two series of conditional stability constants of the complexes have been determined in our experiments: one set of the conditional stability constants, αL,i, related to 1 M nitrate media, whereas the other, βL,i, – to aqueous solutions of ionic strength I = 1 M, where the complexation by nitrates was taken into account. In the latter case, when the effect of the actinide complexation by nitrates was deducted, the conditional stability constants, βL,1, of the actinide complexes with SO3-Ph-BTP4– increase in the order UO22+ < Am3+ < Th4+ < Pu(IV), in accordance with the increasing z/r2 ratio (where z is the formal charge and r is the radius of the metal ion). The analysis of the βL,i values suggests that the electrostatic effects play the major role in the formation of the complexes between the poly-N-dentate ligands and actinides ions.Concerning the complexation of Am3+ with the tri-N-dentate SO3-Ph-BTP4– ligand, if we compare our results with the literature values for the analogous Cm3+ complexes studied by a spectroscopic (TRLFS) technique, the stability constants of 1:1 and 1:2 complexes of Am3+ are much lower, and its 1:3 complex has not been found by the solvent extraction method. The stability constants of the SO3-Ph-BTP and SO3-Ph-BTBP complexes with the actinides(IV) have not been reported yet in literature, therefore such comparison was impossible in this case. However, the expected 1:3 complexes of Pu(IV) and Th(IV) with the SO3-Ph-BTP4– ligand have not been found in our solvent extraction experiments as well. Similarly, only 1:1 Pu and Th complexes with the tetra-N-dentate SO3-Ph-BTBP4– ligand have been found by solvent extraction, in spite of that the 1:2 complexes were also expected. These surprising results could be a result of oversimplification of the used model of extraction, and should be completed by further spectroscopic studies to identify all the complexes formed in the two-phase system studied. Nevertheless, the stability constants determined in the solvent extraction experiments (“practical” stability constants) allow us to correctly describe and to predict the behaviour of metal ions in such two-phase systems.

Submitted by isabela.moljf@hotmail.com (isabela.moljf@hotmail.com) on 2017-05-08T14:44:31Z No. of bitstreams: 1 lippyfariamarques.pdf: 5076100 bytes, checksum: 2953e513680692299734c5fd00a57c88 (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-05-17T13:43:56Z (GMT) No. of bitstreams: 1 lippyfariamarques.pdf: 5076100 bytes, checksum: 2953e513680692299734c5fd00a57c88 (MD5) / Made available in DSpace on 2017-05-17T13:43:56Z (GMT). No. of bitstreams: 1 lippyfariamarques.pdf: 5076100 bytes, checksum: 2953e513680692299734c5fd00a57c88 (MD5) Previous issue date: 2010-03-05 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho consistiu na síntese e caracterização de complexos de metais de transição, especialmente os íons metálicos da primeira série de transição, Cu2+, Co2+ e Zn2+, contendo o ânion dicarboxilato 2,6-piridinodicarboxilato bem como os ligantes nitrogenados rígido e flexível: 4,4’-bipiridina (BIPY) e 1,3-bis(4-piridil)propano (BPP). Todos os compostos sintetizados foram caracterizados por análise elementar (CHN), análise termogravimétrica (TG), espectroscopia vibracional na região do infravermelho (IV) e difração de raios X de monocristal. O capítulo 1 abrange uma breve introdução sobre Polímeros de Coordenação. Adicionalmente, incluiu-se uma apresentação sobre Química Supramolecular seguido de uma apresentação sobre o ligante carboxilato e os ligantes nitrogenados utilizados neste trabalho, destacando a intensa pesquisa na área. No capítulo 2 descreve-se a síntese do sal de sódio derivado do ácido dicarboxílico, bem como dos seis complexos contendo o ligante nitrogenado 1,3-bis(4-piridil)propano e o ligante nitrogenado BIPY. Estes complexos foram formulados como [Cu(2,6-PDC)(2,6-PDCH2)].3H2O (1), [Cu2 (μ-BPP) (2,6-PDC)2(H2O)2]. 2H2O (2), {[Co(H2O)4 (BPP)] [Co(2,6-PDC)2]. H2O}n (3) e (H2BPP) [Zn(2,6-PDC)2].4H2O (4), [ Co2 (μ-BIPY) (2,6-PDC)2(H2O)4]. 2H2O (5) e [Cu2(μ-O2CCH2C4H3S)4(Bipy)]n (6). O capítulo 3 relaciona-se com a caracterização dos complexos contendo o ligante nitrogenado 1,3-bis(4-piridil)propano. Os complexos (2) e (3) tiveram suas estruturas determinadas por difração de raios X de monocristal. O complexo (2) é homobimetálico com dois centros de Cu(II) em geometria pirâmide de base quadrada distorcida conectados através do ligante BPP em ponte. Por outro lado, o composto (3) apresenta uma porção complexa aniônica formada por um centro de Co(II) e dois ânions piridinodicarboxilatos e uma cadeia polimérica catiônica, constituída por íons Co(II) e ligantes BPP em ponte. Em ambos os casos um sistema supramolecular 3-D é gerado através de ligações de hidrogênio. Os dados analíticos e espectroscópicos para o composto (4) sugerem a formação de um complexo formado por duas porções. A porção aniônica é formada por dois ligantes 2,6-piridinodicarboxilatos coordenados de forma tridentada através da coordenação (O-N-O) ao centro de Zn(II) e estabilizando a carga um ligante nitrogenado BPP duplamente protonado. Esse tipo de estrutura é bem suportado por vários exemplos da literatura. O capítulo 4 engloba a caracterização dos complexos contendo o ligante nitrogenado rígido 4,4’-bipiridina (BIPY). Os complexos (5) e (6) tiveram suas estruturas determinadas por difração de raios X de monocristal. No complexo (5) temos a formação de um composto binuclear onde o ligante nitrogenado BIPY atua em ponte entre os sítios metálicos de Co(II) que por sua vez se encontram coordenados de modo tridentado ao ânion 2,6-piridinodicarboxilato e duas moléculas de água culminando em uma geometria octaédrica para o centro metálico. A natureza 3-D é evidenciada através de ligações de hidrogênio do tipo O – H...O. No composto (6) verifica-se que cada centro metálico adota uma geometria pirâmide de base quadrada na qual a base é formada pelos oxigênio do grupos carboxilato e a posição apical ocupada por um átomo de nitrogênio proveniente do ligante BIPY, que atua em ponte entre os sítios de Cu(II), originando uma cadeia polimérica unidimensional. O presente trabalho revela um grande interesse no estudo da Química Supramolecular, abrangendo importantes conteúdos em Química Inorgânica Supramolecular propondo-se diferentes rotas sintéticas para obtenção das estruturas supramoleculares. / This work describes the synthesis and characterization of transition metal complexes, especially the metallic ions from the first row, Cu2+, Co2+ and Zn2+, containing the 2,6-pyridinedicarboxylate anion as well as the rigid and the flexible nitrogen ligands, 4,4’-bipyridine (BIPY) and 1,3-bis(4-pyridil)propane (BPP). All the compounds were characterized by means of elemental analysis (CHN), thermal analysis (TG), infrared spectroscopy (IR) and single crystal X-ray diffraction analysis. Chapter 1 involves a brief introduction about Coordination Polymers. In addition a presentation about Supramolecular Chemistry, carboxylate anions and nitrogen ligands used in this work, is include enphatizing the intensive research in this area. In chapter 2, the synthesis of the sodium salt derived from the dicarboxylic acid, as well as of the six complexes containing the nitrogen ligands 1,3-bis(4-pyridil)propane and 4,4’-bipyridine are described. These complexes were named [Cu(2,6-PDC)(2,6-PDCH2)].3H2O (1), [Cu2 (μ-BPP) (2,6-PDC)2(H2O)2]. 2H2O (2), {[Co(H2O)4 (BPP)] [Co(2,6-PDC)2]. H2O}n (3) e (H2BPP) [Zn(2,6-PDC)2].4H2O (4), [ Co2 (μ-BIPY) (2,6-PDC)2(H2O)4]. 2H2O (5) e [Cu2(μ-O2CCH2C4H3S)4(Bipy)]n (6). Chapter 3 presents the characterization of the complexes containing the nitrogen ligand 1,3-bis(4-pyridil)propane. Complexes (2) and (3) had their structures determined by single crystal X-ray analysis. Complex (2) is homobimetallic were two Cu(II) centers in a distorted square-piramide geometry, connected by a BPP ligand in the bridging mode. On the other hand, compound (3) presents an anionic moiety, formed by a Co(II) center and two pyridinedicarboxylate anions and a cationic polymeric chain, formed by Co(II) ions and bridging BPP ligands. In both cases, a 3-D supramolecular array is generated through hydrogen bondings. The analytical and spectroscopic data for compound (4) suggest the formation of an ionic complex, in which the anionic moiety contains two 2,6-pyridinedicarboxylate anions coordinated to the Zn(II) center in the tridentate (ONO) fashion. The nitrogen ligand BPP is protonated, (H2BPP2+) estabilizing the anionic unit. This type of structure is well supported by several examples from literature. Chapter 4 describes the characterization of the complexes containing the rigid nitrogen ligand 4,4’-bipyridine (BIPY). Complexes (5) and (6) have had their structures determined by single crystal X-ray diffraction analysis. Complex (5) is homobinuclear in which the nitrogen ligand BIPY bridges two Co(II) sites that are also coordinated by 2,6-pyridinedicarboxylate anion in the tridentate mode as well as by two water molecules, in an distorted octahedral geometry. The 3-D supramolecular nature of the system is achievied through O – H…O hydrogen bondings. In compound (6) it can be noticed that each metal center adopts the distorted square-pyramide geometry in which the base is formed by the oxygen atoms from the carboxylate groups and the apical positions is occupied by nitrogen atom from BIPY ligand. The BIPY ligands bridge the Cu(II) sites, generating a one-dimensional polymeric chain. This work shows a great interest in the study of Supramolecular Chemistry, covering important content in Supramolecular Inorganic Chemistry proposing different synthetic routes to obtain of the supramolecular structures.

Catalysis, which is primarily a molecular phenomenon, is an important field of chemistry because it requires the chemical conversion of molecules into other molecules. It also has an effect on many fields, including, but not limited to, industry, environment and life Science[1]. Surface Organometallic Chemistry is an effective methodology for Catalysis as it imports the concept and mechanism of organometallic chemistry, to surface science and heterogeneous catalysis. So, it bridges the gap between homogenous and heterogeneous catalysis[1]. The aim of the present research work is to study the effect of Nitrogen surface ligands on the activity of Alkane, Propane in particular, metathesis. Our approach is based on the preparation of selectively well-defined group (VI) transition metal complexes supported onto mesoporous materials, SBA15 and bearing amido and/or imido ligands. We choose nitrogen ligands because, according to the literature, they showed in some cases better catalytic properties in homogenous catalysis in comparison with their oxygen counterparts[2]. The first section covers the modification of a highly dehydroxylated SBA15 surface using a controlled ammonia treatment. These will result in the preparation of two kind of Nitrogen surface ligands: - One with vicinal silylamine/silanol, (≡SiNH2)(≡SiOH), noted [N,O]SBA15 and, - Another one with vicinal bis-silylamine moieties (≡SiNH2)2, noted [N,N]SBA15[3]. The second section covers the reaction of Schrock type Tungsten Carbyne [W(≡C- tBu)(CH2-tBu)3] with those N-surface ligands and their characterizations by FT-IR, multiple quantum solid state NMR (1H, 13C), elemental analysis and gas phase analysis. The third section covers the generation of the active site, tungsten hydride species. Their performance toward propane metathesis reaction using the dynamic reactor technique PID compared toward previous well-known catalysts supported on silica oxide or mesoporous materials[4]. A fairly good turn over number (TON = 43) has been obtained following hydrogen treatment of tungsten alkylidyne supported on [N,O] SBA151100, in comparison with TON of zero in the obtained with [N,N] SBA15 and classical SiO2 silica support. Therefore, the cooperation between silylamine and silanol in close vicinity are required to improve the efficiency of the catalyst in the metathesis of propane.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / In this work a theoretical study was carried out to investigate the spectroscopic properties of trivalent europium complexes. The study was divided into two parts. The first one was the study of the luminescent efficiency of five complexes which had as ligands β-diketones and pyrazole. Pyrazole modifications were made promoting a gradual increase in the amount of fluorine atoms in the search for systems with greater luminescence. The second part was the study of structural elucidation and luminescent efficiency of two Eu3+ complexes, which showed as ligand the molecule of ibuprofen and methylbipyridine. The difference between the two systems was that in one complex the methyl group of bipyridine was in the meta position and in the other in the para position. Semiempirical methodologies such as the Sparkle models, the INDO/S-CIS method, the Judd-Ofelt theory and the energy transfer models proposed by Malta et al were used to certify this. The theories and models used to treat the spectroscopic properties of these systems are implemented in the LUMPAC - Luminescence Package, which was used in this study. In the first part, an evaluation of calculation models of the ground state geometry more suitable for the study and from comparisons with crystallographic structures the model that presented smaller error was the Sparkle/PM3. From the results obtained, it has been seen that the luminescence intensity of the Eu3+ complexes increases when the C-H bonds are replaced by C-F bonds, and more strongly when CF2 groups are added. Further extension in the length of the fluorinated chain greatly decreases the rate of nonradiative decay and increases the rate of radiative decay, thereby increasing the quantum efficiency of the complex. The results obtained were theoretically compared with the experimental results and showed good agreement. In the second part of the work, no evaluation of the geometry calculation model was performed, since it is a system that does not have certain crystallographic structures. Thus, the RM1 model was used to optimize the geometry, since it is a recent model that satisfactorily treats lanthanide systems. The results obtained did not show much difference, that is, the position of the methyl group in the meta or para position in the bipyridine linker does not cause considerable effect on the coordination polyhedron. However, they presented higher radiative decay rates than the rates of non-radiative decay and high quantum efficiency. Finally, the good agreement between the theoretical results and the experimental results is a strong indicatio / Neste trabalho foi realizado um estudo teórico para a investigação das propriedades espectroscópicas de complexos de európio trivalente. O estudo foi dividido em duas partes. Na primeira foi feito o estudo da eficiência luminescente de cinco complexos os quais tinham como ligantes β-dicetonas e pirazol, sendo que no pirazol foram realizadas modificações promovendo um aumento gradativo na quantidade de átomos de flúor na busca por sistemas com maior luminescência. Na segunda parte foi feito o estudo de elucidação estrutural e da eficiência luminescente de dois complexos de Eu3+, os quais apresentavam como ligante a molécula de ibuprofeno e a metilbipiridina. A diferença entre os dois sistemas era que em um complexo o grupo metil da bipiridina estava na posição meta e no outro na posição para. Para isto, foram utilizadas metodologias semiempíricas, tais como os modelos Sparkle, o método INDO/S-CIS, a teoria de Judd-Ofelt e os modelos transferência de energia propostos por Malta e colaboradores. As teorias e modelos utilizados para tratar das propriedades espectroscópicas destes sistemas, estão implementados no pacote computacional LUMPAC – Luminescence Package, o qual foi utilizado neste estudo. Na primeira parte, fez-se uma avaliação dos modelos de cálculo da geometria do estado fundamental mais adequada para o estudo e a partir de comparações com estruturas cristalográficas o modelo que apresentou menor erro foi o Sparkle/PM3. A partir dos resultados obtidos, foi visto que a intensidade de luminescência dos complexos de Eu3+ aumenta quando as ligações C-H são substituídas por ligações C-F, e mais fortemente quando grupos CF2 são adicionados. A extensão adicional no comprimento da cadeia fluorada diminui fortemente a taxa de decaimento não radiativo e aumenta a taxa de decaimento radiativo, aumentando dessa maneira a eficiência quântica do complexo. Os resultados obtidos teoricamente foram comparados com os resultados experimentais e apresentaram boa concordância. Na segunda parte do trabalho, não foi realizado avaliação de modelo de cálculo de geometria, por se tratar de sistemas que não apresentam estruturas cristalográficas determinadas. Assim, foi utilizado o modelo RM1 para otimização da geometria, por se tratar de um modelo recente que trata de maneira satisfatória sistemas lantanídicos. Os resultados obtidos não apresentaram muita diferença, ou seja, a posição do grupo metil na posição meta ou para no ligante bipiridina não causa efeito considerável sobre o poliedro de coordenação. No entanto, apresentaram taxas de decaimento radiativo maiores do que as taxas de decaimento não radiativo e elevada eficiência quântica. Por fim, a boa concordância entre os resultados teóricos e os resultados experimentais é um forte indício que as estruturas propostas correspondem aos sistemas sintetizados. / São Cristóvão, SE