The research presented in this dissertation focuses on chiral BINOL metal phosphatephosphoric acid catalyzed enantioselective additions of phosphorus and sulfur nucleophiles to imines and epoxides. In chapter 2, we reported a new method to synthesize chiral amino phosphine oxides. The reaction combines N-substituted imines and diphenylphosphine oxide catalyzed by chiral magnesium 9-antryl phosphate. A wide variety of aliphatic and aromatic aldimines substituted by electron neutral benzhydryl or dibenzocycloheptene groups were excellent substrates for the addition reaction. The imines protected with dibenzocycloheptene protecting group provided better enantioselectivity than those protected with benzhydryl group, while both imines gave comparable yields. Also, the substituted diphenylphosphine oxides were excellent nucleophiles obtaining chiral α-amino phosphine oxides in good yields and enantioselectivities. In chapter 3, we reported the first catalytic asymmetric method to prepare enantioenriched N,S-acetals catalyzed TRIP phosphoric acids. The reaction combined N-acyl imines with thiols to generate products in excellent yield and enantioselectivity. Electron-rich and electron-deficient aromatic N-acyl imines were excellent substrate for the addition reaction. A wide range of aliphatic and aromatic thiols obtained the N,S-acetals in excellent yields and enantioselectivities. The TRIP phosphoric acid was found to be an extremely efficient catalyst for the transformation, resulting in asymmetric induction at extremely low catalyst loading. In chapter 4, a highly enantioselective method for desymmetrization of meso-epoxides using thiols catalyzed by substituted BINOL lithium phosphate is reported. This is the first example of epoxide activation using metal phosphate is reported. Various five and six membered aliphatic cyclic meso-epoxides were excellent substrates for the desymmetrization reaction; aromatic acyclic epoxides also reacted with excellent yield and asymmetric induction. Similarly electron rich and electron deficient aromatic thiols obtained the β-hydroxyl sulfides in excellent yields and enantioselectivities.

This thesis reports progress in three major aspects of σ-bonded organometallic porphyrins that are described in the published papers found in chapters 4, 5 and 6. meso-Iodoporphyrins, which were prepared in a rapid, selective and high yielding methodology from the respective 1-palladioporphyrins or bromoporphyrins, are important starting materials for further functionalisations of porphyrins. Their utility was confirmed in a palladium-catalysed coupling reaction and this novel synthetic strategy could potentially be applied for iodine/bromine exchange on other organic substrates.. A 1-palladioporphyrin was also utilised to optimise the reaction conditions leading to the formation of porphyrinylphosphine oxides. This synthetic strategy simplified the challenging optimisation of the palladium-catalysed reaction and has great potential to be applied in other catalytic processes. Subsequently a suite of porphyrinylphosphine oxides was prepared under the optimised catalytic conditions. These macrocycles, which represent a new class of porphyrins, were isolated cleanly in very high yields. Detailed spectroscopic investigations as well as X-ray single crystal analysis demonstrated their structures unambiguously and established their potential as ligands for supramolecular chemistry. The coordinating properties of phosphine oxides in general and porphyrinylphosphine oxides in particular, towards Mg(II) centred porphyrins were examined in further experiments. Triphenylphosphine oxide showed a strong affinity towards Mg(II) porphyrins and the calculated displacement constant of 5.3 × 105 M-1 was two orders of magnitude larger than any other Mg(II) porphyrin-ligand binding constant reported thus far. Di- and triporphyrin arrays consisting of Mg(II) porphyrin coordinated to free base and Ni(II) porphyrinyl mono- and bis-phosphine oxides were also prepared in high yields. Spectroscopic studies indicated that these porphyrin oligomers exhibit strong inter-porphyrin electronic interaction. A Mg(II) porphyrinylphosphine oxide dimer was also isolated in a satisfactory yield. The large self-association constant of 5.5 × 108 M-1 confirmed the strong affinity of porphyrinylphosphine oxides towards Mg(II) porphyrins and established these complexes as the first strongly bound synthetic Mg(II) porphyrin analogues of the "special pair" of the photosynthetic reaction centre.

Title: Comlpexes of aminoalkylphosphineoxides Author: Bence Mészáros Department: Department of Inorganic Chemistry, Faculty of Science UK Supervisor: doc. RNDr. Vojt ch Kubí ek, Ph.D. Supervisor's e-mail address: kubicek@natur.cuni.cz Three selected aminoalkylphosphine oxides were synthesized: Aminomethyl(diphenyl)phosphine oxide, N-piperidylmethyl(diphenyl)phosphine oxide, N,N-diethylaminomethylbis(hydroxomethyl)phosphine oxide. All prepared substances were characterized by NMR spectroscopy and mass spectrometry. The aminomethyl(diphenyl)phosphine oxide and N-piperidylmethyl(diphenyl)phosphine oxide were obtained in the solid state as single crystals and their structure was determined by X-ray analysis. Acid-base and complexing properties of the studied compounds were studied by potentiometric titration and NMR titration. Protonation constants of all three compounds were obtained, stability constants were not determined because of the low solubility of the complexes in water or low stability of the complexes. The structure of the aminomethyl(diphenyl)phosphine oxide complex with Cu2+ was determined by X-ray analysis. Keywords: complexes, organophosphorus synthesis, phosphine oxides, acid-base and complexation properties

Dans la thèse de doctorat, nous avons développé une approche efficace pour la modification rapide d'oxydes d'arylphosphines via la fonctionnalisation de liaisons C-H en position ortho du groupement P=O catalysée par le ruthénium (II) en présence des alcènes. Intéressement, l'ajustement du pH du milieu réactionnel permet de contrôler la sélectivité de la réaction à savoir alkylation or oléfination. La réduction des oxydes de phosphines fonctionnalisées permet la formation d'arylphosphines portant un carboxylate flexible. Dans le second objectif, un couplage C(sp3)–H /N-H oxydatif catalysé par le cuivre a permis l'alkylation d'hétérocycles à partir de (cyclo alcanes abordables. Ce protocole implique la formation de liaisons C (sp3)–N via une voie radicalaire générée par un clivage homolytique du peroxyde de di-tert-butyle et le piégeage du ou des radicaux par des catalyseurs au cuivre. Dans une troisième partie, nous avons utilisé ces processus radicalaires pour la fonctionnalisation le liassions C(sp3)–H benzylique d'oxyde de 2-alkylpyridines. Ces transformations impliquent un processus en cascade : estérification oxydative catalysée par le cuivre suivie d'un transfert d'atome d'oxygène. Enfin, des dérivés tosylés de pyridin-2-ylméthyl ont été obtenus avec des rendements élevés à partir des oxide de 2-alkylpyridines grâce à un réarrangement sigmatropic [3,3] du produit d'addition entre les oxides de 2-alkylpridine avec des chlorures de chlorure de benzènesulfonyles. De plus, les alkylnitrones subissent également ce réarrangement sigmatropique [3,3] pour donner des cétones α-tosylées après hydrolyse. / In the first chapter, we have developed an efficient approach for the fast modification of arylphosphine oxides using ruthenium(II)-catalyzed C–H bond functionalization with alkenes. Interestingly, we have found that the selectivity of the reaction, namely alkylation versus alkenylation, is depending on the reaction pH. The reduction of the phosphine oxide allows the formation of aryl phosphines bearing a flexible pendent carboxylate. In the second objective, a copper-catalyzed oxidative C(sp3)–H/N–H coupling of NH-heterocycles with affordable (cyclo)alkanes was developed. This protocol involved C(sp3)–N bond formation via a radical pathway generated by a homolytic cleavage of di-tert-butyl peroxide and trapping of the radical(s) by copper catalyst.In a third part, benzylic C(sp3)–H acyloxylation of 2-alkylpyridine, 2-alkylpyrazine and 2-alkylthiazole compounds was achieved using simple aldehydes via a copper-catalyzed tandem reaction, involving oxidative esterification followed by O-atom transfer. Finally, pyridin-2-ylmethyl tosylate derivatives are obtained in high yields from 2-alkylpyridine N-oxides via a [3,3]-sigmatropic rearrangement of the adduct between 2-alkylpridine N-oxides with benzenesolfonyl chlorides. Moreover, alkylnitrones also underwant [3,3]-sigmatropic rearrangement to give α-tosylated ketones after hydrolysis.

Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-08-07T15:46:16Z No. of bitstreams: 1 arquivototal.pdf: 5525294 bytes, checksum: b7714e7665b3af997613f352395d6e2b (MD5) / Made available in DSpace on 2017-08-07T15:46:16Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 5525294 bytes, checksum: b7714e7665b3af997613f352395d6e2b (MD5) Previous issue date: 2014-09-03 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This work reports spectroscopic and structural investigations of the complexes presenting the formulas [Ln(TTA)3L2], [Ln(DBM)3L], [Ln(TTA)2(NO3)L2], [Ln(DBM)2(NO3)L2] and [Ln(DBM)(NO3)2(HMPA)2], where Ln: Eu3+ or Tb3+, TTA: 2-thenoyltrifluoroacetonate, DBM: dibenzoylmethanate and L: HMPA (hexamethylphososphoramide) or TPPO (Triphenylphosphine oxide). The compounds were characterized by complexometric and elemental analysis and single crystal X-ray diffraction. The spectroscopic properties of the complexes were studied by diffuse reflectance and luminescence spectroscopies. Formation of positronium in the complexes were also investigated. In order to obtain a synergy between theory and experiment, DFT calculations were performed, for geometry optimization and to obtain DBM triplet states energies, using B3LYP, B97D, M06-2X, PBE1PBE, CAM-B3LYP and ω-B97XD functionals, in both gas phase and in acetone solvent. X-ray data showed that the replacement of DBM molecules by nitrate ions promotes stronger intramolecular interactions, which influence the compounds melting points. The diffuse reflectance and excitation spectra suggest the presence of ligant-to-metal charge transfer states (LMCT) of low energy in DBM containing Eu3+ complexes. The replacement of DBM ligands by nitrate ions decrease the energy of these LMCT states. This decrease is duo to the lower polarizability of the nitrate ion which promotes a greater charge donor effect on the other ligands, reducing the energy of the LMCT state. Positron annihilation results showed that positronium formation in compounds containing both DBM and phosphine oxides decreases when the former are replaced by nitrate ions, due to the increase of electron density donation from the ligands to the metal center, decreasing the phosphinoxides positronium formation capacity. DFT calculation provided relatively satisfactory results for geometry optimization and in obtaining DBM triplet states energies. These results indicate that the replacement of B-diketonate ligands by less polarizable species, such as nitrate, has a great influence on the structural and spectroscopic properties of the investigated compounds. / Este trabalho reporta investigações espectroscópicas e estruturais de complexos de fórmulas [Ln(TTA)3L2], [Ln(DBM)3L], [Ln(TTA)2(NO3)(TPPO)2], [Ln(DBM)2(NO3)L2] e [Ln(DBM)(NO3)2(HMPA)2], em que Ln: Eu3+ ou Tb3+, TTA: 2-tenoiltrifluoroacetonato, DBM: dibenzoilmetanato e L: HMPA (hexametilfosforamida) ou TPPO (Trifenilfosfinóxido). Os compostos foram caracterizados por análises complexométricas e elementar e difração de raios X de monocristal. As propriedades espectroscópicas dos complexos foram estudadas através de espectroscopia de reflectância difusa e de luminescência. O processo de formação de positrônio nos complexos também foi investigado. No intuito de obter uma sinergia teoria-experimento, foram realizados cálculos DFT, para otimização de geometria e obtenção de estados tripletos do DBM, utilizando os funcionais B3LYP, B97D, M06- 2X, PBE1PBE, CAM-BγLYP e ω-B97XD, em fase gasosa e no solvente acetona, Os dados de estruturas de raios X mostraram que a substituição de moléculas de DBM por íons nitrato promove a existência de interações intermoleculares mais fortes o que tem uma influência sobre o ponto de fusão dos compostos. Os espectros de reflectância difusa e de excitação sugerem a presença de estados de transferência de carga ligantemetal (TCLM) de baixa energia em complexos de Eu3+ contendo o ligante DBM, com um abaixamento na energia desses estados à medida que os ligantes DBM são substituídos por íons nitrato. Isso é explicado considerando que a menor polarizabilidade do íon nitrato provoca um maior efeito doador de carga nos outros ligantes, diminuindo a energia do estado TCLM. Os resultados de aniquilação de pósitron mostraram que a formação de positrônio em compostos com ligantes DBM e fosfinóxidos diminui quando os primeiros são substituídos por íons nitrato, devido ao aumento da doação de densidade eletrônica dos ligantes para o centro metálico, diminuindo a capacidade formadora dos fosfinóxidos. Os cálculos teóricos DFT forneceram resultados relativamente satisfatórios para a otimização de geometrias dos complexos e para a obtenção de energias dos estados tripletos do ligante DBM. Esses resultados indicaram que a substituição de ligantes B-dicetonatos por espécies menos polarizáveis, como o nitrato, tem grande influência nas propriedades estruturais e espectroscópicas dos compostos estudados.

The structural, electronic, and optical properties of a series of organic pi-conjugated polymer, oligomer, or molecular materials of interest for applications in organic electronics are described. For this purpose, quantum-chemical techniques ranging from Density Functional Theory to Hartree-Fock ab initio and semiempirical methods are used to evaluate the charge-transport, charge-transfer, and electroluminescence properties of pi-conjugated organic materials. First, the effect of electronic polarization on the charge-transport parameters of organic semiconductors is discussed. A generalized methodology based on a basis set orthogonalization procedure is developed to determine reliable charge-transport characteristics. The charge-transport parameters of a number of organic semiconductors such as oligoacenes and derivatives are studied with this methodology. Then, triplet emitters, in particular iridium complexes, that achieve high efficiency electroluminescence in organic light-emitting diodes are discussed. The effects of ligand substitution and orientation on the luminescent properties of iridium compounds are investigated in order to develop structure-properties relationships. The emission properties of these complexes are found to be governed by an interplay between metal-to-ligand charge transfer excitations and ligand-centered and/or interligand excitations. The extent of mixing of these various excitations turns out to be highly dependent on the nature of the substituents. Design strategies to shift the emission color towards deep blue are proposed. Finally, several classes of materials acting as hosts for phosphorescent emitters are studied. It is shown that restricting the conjugation length leads to high energy gap host materials suitable for blue phosphorescent emitters.

Depuis le début des années 2000, les Oxydes de Phosphine Secondaire (OPS) connaissent un regain d'intérêt en catalyse comme préligands des métaux de transitions. Alors que de nombreux complexes organométalliques associés à des OPS ont été préparés, caractérisés et utilisés en catalyse homogène, les complexes correspondant du ruthénium sont plus rares.Nous nous sommes intéressés à la synthèse et la caractérisation de nouveaux complexes de ruthénium(II) comportant un (ou plusieurs) ligand acide phosphineux (AP) (forme tautomère d'un OPS) puis au rôle du ligand dans un cycle catalytique. Le traitement de différentes sources de ruthénium par des OPS a permis d'isoler des séries de complexes de ruthénium [Ru]/OPS (coordination par l'oxygène) et [Ru]/AP (coordination par le phosphore). L'activité catalytique de ces complexes bien définis a été étudiée dans des réactions d'activation de liaisons C-H et de cycloisomérisation à partir d'alcynes ou d'ynamides. Lors de ces études, il a été montré l'influence des paramètres stéréoélectroniques du ligand lié au ruthénium au cours du processus catalytique.En marge de ces travaux, dans la continuité de notre intérêt pour la réactivité des ynamides, nous avons développé une nouvelle réactivité des ynamides avec les 1,3-dicétones cycliques catalysée au ruthénium, à l'or ou au palladium pour la synthèse d'alpha-alcoxy-énamides. / The past decade has witnessed a renewed interest for Secondary Phosphine Oxides (SPO) in catalysis as preligands of transition metals. While the coordination chemistry and catalytic activity of these species have been mainly studied with palladium and platinum, only few examples with ruthenium have been reported so far.We investigated the synthesis of new ruthenium(II) complexes associated to one or two phosphinous acid ligand (PA) (SPO tautomer) which were fully characterised. Then we were interested in the role played by the ligand during the catalytic cycle. The use of different ruthenium sources allowed us to isolate [Ru]/SPO complexes (oxygen coordinated) and [Ru]/PA complexes (phosphorous coordinated). We evaluated the catalytic activities of these well-defined complexes in C-H bond activation and cycloisomerisation from alkynes or ynamides. During the course of these studies, the influence of ligand stereoelectronic parameters in the catalytic process have been demonstrated.Moreover, in a side project, we explored a new reactivity of ynamides with cyclic 1,3-diketones catalysed by palladium, cationic gold or ruthenium complexes. This reactivity gives access to alpha-alkoxysubstituted enamides.