Este estudo se baseou em dados extraídos de um corpus paralelo composto por textos originais em inglês de artigos da Revista National Geographic, suas respectivas traduções publicadas em português na National Geographic Brasil, e os textos traduzidos antes da revisão para publicação. O objetivo foi cotejar os três textos a fim de identificar, na tradução, elementos que promovem a produção de um texto natural e fluente, que reflete o uso mais corrente na língua. Sua inserção no âmbito da lingüística de corpus se deu por essa permitir um estudo lingüístico descritivo e não prescritivo da língua e por se voltar não só para as palavras, estruturas ou usos possíveis na língua mas também o que é provável que ocorra, isto é, a diferença entre o que os falantes podem dizer e o que na verdade dizem. Esse cotejo possibilitou o levantamento de aspectos lingüísticos que afetam a naturalidade e fluência do texto, como a fraseologia típica na língua de chegada, suas colocações naturais, suas próprias expressões fixas, que refletem um modo preferido de se expressar de cada comunidade lingüística. Esses aspectos estão intimamente relacionados à convencionalidade, que abrange aquilo que é consolidado pelo uso, constituindo muitas vezes fonte de dificuldade ao \"tradutor ingênuo\" que pode não perceber que dentre formas possíveis existe aquela mais provável de ocorrer. Dentre os elementos levantados, selecionou-se a tradução dos advérbios terminados em *ly em inglês, nem sempre traduzidos por advérbios terminados em *mente em português, procurando compreender essa opção dentro do âmbito da convencionalidade. Essas opções nem sempre são ilustradas em dicionários, constituindo a pesquisa baseada em corpora, tanto paralelos quanto monolíngües, um recurso valioso ao tradutor seja para mostrar estratégias empregadas por outros tradutores profissionais como para conscientizá-lo de um uso consagrado na língua. / This study was based on data collected from a parallel corpus composed of original texts in English of articles from National Geographic magazine, and their respective translations in Portuguese as published in National Geographic Brazil and the texts translated before their revision for publication. The aim was to compare the three texts in order to identify, in translation, elements that enable the production of a text which sounds natural and fluent, reflecting the current use by the speakers. Corpus Linguistics was chosen as an approach for the research since it allows a descriptive rather than a prescriptive study of the language and is typically concerned not only with what words, structures or uses are possible in a language, but also with what is probable, likely to occur, the difference between what the speakers can say and what they actually say. This comparison brought to light linguistic features which might affect naturalness and fluency of a text, as the typical phraseology in the target-language, its natural collocations and its own fixed expressions, which reflect a preferred way of a community of saying things. These aspects are closely related to conventionality, which encompasses that which is attested by the use, and represent precisely where the difficulties lie for the \"innocent translator\", who might not notice that among a range of possible forms there is one which is more likely to occur. Among the elements found, one was particularly investigated, namely, the translation of adverbs ending in *ly in English , not always translated by adverbs ending in *mente in Portuguese, with a view to understand this option within the idea of conventionality. These options are not frequently displayed in dictionaries, which makes corpus-based research , either using parallel corpora or monolingual corpora, an invaluable resource to translators, in eliciting strategies employed by other professional translators and in bringing awareness to an attested use in language.

La communication électronique dans des complexes dinucléaires du ruthénium peut être caractérisée soit par le couplage électronique Vab dans le système à valence mixte (RuII-RuIII), soit par le couplage magnétique J dans le système homovalent paramagnétique (RuIII-RuIII). L'objectif de ce travail était d'obtenir une famille de composés en faisant varier la longueur du ligand pontant et de mesurer les interactions électronique et magnétique afin d'établir une corrélation entre J et Vab.<br />Une première famille de complexes dinucléaires du ruthénium [{RuII(tpy)(acac)}2(µ-L)] (où tpy = 2,2'-6',2''-terpyridine, acac = acétylacétonate et L est un ligand pontant dicyanamide) a été synthétisée. Ces complexes, bien que prometteurs pour la mesure des couplages électroniques et magnétiques, n'ont pas pu être caractérisés et étudiés complètement en raisons des problèmes de solubilité rencontrés.<br />Une deuxième famille de composés [{RuII(tpy)(thd)}2(µ-L)] (où thd = 2,2,6,6-tétraméthylheptanedione), plus solubles de par la présence de groupements tert-butyles, a ensuite été synthétisée, la distance métal-métal variant entre 12,0 et 25,1 Å. Les formes à valence mixte RuII-RuIII de ces complexes ont été générées par électrochimie et le couplage électronique Vab déterminé par spectroscopie UV-Vis-Proche IR. On retrouve une décroissance exponentielle de ce paramètre avec la distance métal-métal. Les formes homovalentes paramagnétiques RuIII-RuIII ont été générées chimiquement et/ou électrochimiquement, des mesures de susceptibilité magnétique et des études RPE ont permis la détermination du paramètre de couplage magnétique J et la mise en évidence d'une loi de décroissance exponentielle de ce paramètre avec la distance métal-métal.<br />Le complexe le plus court de cette famille [{RuII(tpy)(thd)}2(µ-dicyd)] (où dicyd = dicyanamidobenzène) présente un comportement très différent. Des études électrochimiques, spectroscopiques (UV-Vis-PIR, RPE), magnétiques et cristallographiques complétées par des calculs DFT ont mis en lumière la non-innocence du ligand dicyanamidobenzène dans ce type de systèmes. En l'occurrence, celui-ci est oxydé avant les deux ions ruthénium (II).

CoordenaÃÃo de AperfeÃoamento de Pessoal de NÃvel Superior / Os resultados apresentados neste trabalho envolvem a sÃntese de compostos de coordenaÃÃo contendo fosfinas e ligantes redox ativos (ligantes nÃo-inocentes) na esfera de coordenaÃÃo do rutÃnio. Este trabalho està inserido em uma linha de pesquisa do Grupo de BioinorgÃnica que visa, como objetivo final, a aplicaÃÃo dos compostos isolados na catÃlise de reaÃÃes de hidrogenaÃÃo. Durante o desenvolvimento das atividades de doutorado, perÃodo de marÃo de 2010 a janeiro de 2015, foram sintetizados seis (06) compostos inÃditos na literatura, um dos quais sendo classificado como complexo precursor, [RuIICl2(binap)(PPh3)], onde binap = 2,2&#8242;-bis(difenilfosfina)-1,1&#8242;-dinaftaleno. Todos estes compostos foram caracterizados por ressonÃncia magnÃtica nuclear de fÃsforo (RMN 31P{1H}), anÃlise elementar e espectroscopias vibracional na regiÃo do infravermelho e eletrÃnica nas regiÃes do ultravioleta e visÃvel. A despeito das diversas tentativas de formaÃÃo de cristais dos complexos isolados, apenas o composto trans-[RuIICl2(dppb)(opda-Clcat)], onde dppb = 1,4-bis(difenilfosfina)butano e opda-Clcat = 4-cloro-1,2-fenilenodiamina, forneceu cristais passÃveis de anÃlise por difraÃÃo de raios X. A partir dos resultados obtidos durante o perÃodo citado, dois trabalhos foram publicados em periÃdicos indexados (Polyhedron 2010, 29, 3349â3354 e Polyhedron 2012, 31, 104â109) e cinco trabalhos foram apresentados em congressos nacionais e internacionais. Os espectros de RMN 31P{1H} dos compostos sintetizados apresentaram um Ãnico sinal indicando que os Ãtomos de fÃsforo ocupam posiÃÃes equivalentes e trans aos Ãtomos doadores dos ligantes nÃo-inocentes. Apenas o composto trans-[RuIICl2(dppb)(opda-Clcat)] apresentou um dubleto de dubleto que foi atribuÃdo à assimetria do ligante opda-Cl, sendo confirmado pelos dados de difraÃÃo de raios X. Os dados de espectroscopia eletrÃnica indicaram o estado oxidado dos ligantes o-fenilÃnicos apÃs coordenaÃÃo ao centro metÃlico sendo possÃvel, portanto, a observaÃÃo de interaÃÃes de retrodoaÃÃo. Os ensaios de atividade catalÃtica foram monitorados por cromatografia gasosa acoplada à espectrometria de massa utilizando a reaÃÃo padrÃo de hidrogenaÃÃo da molÃcula de acetofenona ao Ãlcool 1-feniletanol. AlÃm dos complexos originalmente apresentados nesta tese, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) e trans-[RuIICl2(PPh3)2(fenantq)](6), onde fenantq e opdaq sÃo, respectivamente, 9,10-fenantrequinona e 1,2-fenilenodiamina, tais ensaios foram, tambÃm, realizados com compostos previamente sintetizados durante a dissertaÃÃo de mestrado e por outros membros do Grupo de BioinorgÃnica, resultando em um total de vinte (20) catalisadores estudados. Destes complexos, dois foram estudados em condiÃÃes heterogÃneas apÃs imobilizaÃÃo sobre esferas hÃbridas de sÃlica/quitosana. Dentre os sistemas estudados, os complexos trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) e cis-[RuIICl2(dppb)(tabq,cat)](16), onde tabq,cat = 3,3â,4,4â-tetraaminobifenil, apresentaram os mais altos valores de conversÃo (> 90%) em todas as condiÃÃes analisadas. Os valores de conversÃo observados para os sistemas heterogÃneos, ~ 60%, embora menores que aqueles calculados para os sistemas homogÃneos em condiÃÃes similares, nÃo representam desvantagem, uma vez que implicam na reduÃÃo da etapa de separaÃÃo. Os compostos que apresentaram maiores valores de conversÃo em meio homogÃneo apresentam, em comum, a presenÃa de ligantes nÃo-inocentes no estado oxidado. Essa observaÃÃo indica a presenÃa de efeitos sinÃrgicos que influenciam na afinidade do substrato, a citar: (i) aumento da acidez de Lewis do metal pela oxidaÃÃo do ligante e (ii) funÃÃo de reservatÃrio de densidade eletrÃnica do ligante redox ativo que permitir o metal estocar (doar) densidade eletrÃnica no (para o) ligante durante as etapas elementares do ciclo catalÃtico, evitando a localizaÃÃo excessiva de carga sobre o metal. / The results presented in this thesis involve the synthesis of coordination compounds containing phosphine ligands and redox active (non-innocent ligands) in the ruthenium coordination sphere. This work is part of a research line of Bioinorganic Group research aimed, as the ultimate goal, the application of the isolated compounds in catalysis of hydrogenation reactions. During the development of PhD activities, from March 2010 to January 2015, six compounds (06) unpublished in the literature were synthesized; one of which being classified as a precursor complex, [RuIICl2(binap)(PPh3)], where binap = 2,2&#8242;-bis(diphenylphosphine)-1,1&#8242;-dinaphthalene. All of these complexes were characterized by means of phosphorous nuclear resonance magnetic (RMN 31P{1H}), elemental analysis, infrared spectroscopy and electronic spectroscopy in the ultraviolet and visible regions. Despite several attempts to produce crystals of the synthesized compounds, only the trans-[RuIICl2(dppb)(opda-Clcat)] complex, where dppb = 1,4-bis(diphenylphosphine)butane and opda-Clcat = 4-cloro-1,2-phenylenediamine, yielded suitable crystals for determination of X-ray structure. From the results obtained during the cited time, two papers were published in indexed journals ((Polyhedron 2010, 29, 3349â3354 and Polyhedron 2012, 31, 104â109) and five works were shown in national and international meetings. The RMN 31P{1H} spectra of the isolated compounds presented only one signal indicating that the phosphorous atoms lie in equivalent positions and trans in relation to the donor atoms of the non-innocent ligands. For the trans-[RuIICl2(dppb)(opda-Clcat)] complex, however, a dublet of dublet was observed and was assigned to the assimetry of the opda-Cl moiety, which was confirmed by X ray diffraction. The electronic spectroscopic data indicated the oxidized state of the o-phenylene ligands upon coordination to the metal atom thus making possible the back-bonding interaction. The catalytic activity assays were monitored by gas chromatography coupled to mass spectrometry using the standard hydrogenation reaction of the alcohol molecule acetophenone to 1-phenyl ethanol. In addition to the complex originally presented in this thesis, [RuIICl2(binap)(PPh3)](1), trans-[RuIICl2(binap)(opda-Clcat)](2), trans-[RuIICl2(binap)(fenantq)](3), trans-[RuIICl2(PPh3)2(opdaq)](5) and trans-[RuIICl2(PPh3)2(fenantq)](6), where fenantq and opdaq are, respectively, 9,10-phenanthraquinone and 1,2-phenylenediamine, such assays were also carried out for compounds which were previously synthesized during the master course and by other researchers of the Bioinorganic Group resulting resulting in a total of twenty (20) studied catalysts. Among these complexes, two were studied in heterogeneous condition upon immobilization on hybrid spheres of silica chitosan. By accounting for all the studied conditions, the highest values of conversion (> 90%) were observed for trans-[RuIICl2(dppb)(Quinone)](10), cis-[RuIICl2(dppb)(opda-Clq)](13), trans-[RuIICl2(dppb)(tabq,cat)](15) and cis-[RuIICl2(dppb)(tabq,cat)](16), where tabq,cat = 3,3â,4,4â-tetraaminobiphenyls. The values of conversion observed for the heterogeneous systems, c.a. 60%, although lower than those calculated for the homogeneous systems under similar conditions, do not constitute a disadvantage, since separation step is no longer needed. The compounds that showed the higher conversion values in homogeneous medium feature in common the presence of non-innocent ligands in the oxidized state. This observation indicates, very probably, two synergistic effects which influence the affinity of the substrate: (i) the increase of the Lewis acidity of the metal by the oxidation of the ligand and (ii) the function of electron density reservoir of the redox active ligand that allows the metal to store (donate) electron density from (to) the ligand during the elementary steps of the catalytic cycle by preventing excessive charge density on the metal.

Este estudo se baseou em dados extraídos de um corpus paralelo composto por textos originais em inglês de artigos da Revista National Geographic, suas respectivas traduções publicadas em português na National Geographic Brasil, e os textos traduzidos antes da revisão para publicação. O objetivo foi cotejar os três textos a fim de identificar, na tradução, elementos que promovem a produção de um texto natural e fluente, que reflete o uso mais corrente na língua. Sua inserção no âmbito da lingüística de corpus se deu por essa permitir um estudo lingüístico descritivo e não prescritivo da língua e por se voltar não só para as palavras, estruturas ou usos possíveis na língua mas também o que é provável que ocorra, isto é, a diferença entre o que os falantes podem dizer e o que na verdade dizem. Esse cotejo possibilitou o levantamento de aspectos lingüísticos que afetam a naturalidade e fluência do texto, como a fraseologia típica na língua de chegada, suas colocações naturais, suas próprias expressões fixas, que refletem um modo preferido de se expressar de cada comunidade lingüística. Esses aspectos estão intimamente relacionados à convencionalidade, que abrange aquilo que é consolidado pelo uso, constituindo muitas vezes fonte de dificuldade ao \"tradutor ingênuo\" que pode não perceber que dentre formas possíveis existe aquela mais provável de ocorrer. Dentre os elementos levantados, selecionou-se a tradução dos advérbios terminados em *ly em inglês, nem sempre traduzidos por advérbios terminados em *mente em português, procurando compreender essa opção dentro do âmbito da convencionalidade. Essas opções nem sempre são ilustradas em dicionários, constituindo a pesquisa baseada em corpora, tanto paralelos quanto monolíngües, um recurso valioso ao tradutor seja para mostrar estratégias empregadas por outros tradutores profissionais como para conscientizá-lo de um uso consagrado na língua. / This study was based on data collected from a parallel corpus composed of original texts in English of articles from National Geographic magazine, and their respective translations in Portuguese as published in National Geographic Brazil and the texts translated before their revision for publication. The aim was to compare the three texts in order to identify, in translation, elements that enable the production of a text which sounds natural and fluent, reflecting the current use by the speakers. Corpus Linguistics was chosen as an approach for the research since it allows a descriptive rather than a prescriptive study of the language and is typically concerned not only with what words, structures or uses are possible in a language, but also with what is probable, likely to occur, the difference between what the speakers can say and what they actually say. This comparison brought to light linguistic features which might affect naturalness and fluency of a text, as the typical phraseology in the target-language, its natural collocations and its own fixed expressions, which reflect a preferred way of a community of saying things. These aspects are closely related to conventionality, which encompasses that which is attested by the use, and represent precisely where the difficulties lie for the \"innocent translator\", who might not notice that among a range of possible forms there is one which is more likely to occur. Among the elements found, one was particularly investigated, namely, the translation of adverbs ending in *ly in English , not always translated by adverbs ending in *mente in Portuguese, with a view to understand this option within the idea of conventionality. These options are not frequently displayed in dictionaries, which makes corpus-based research , either using parallel corpora or monolingual corpora, an invaluable resource to translators, in eliciting strategies employed by other professional translators and in bringing awareness to an attested use in language.

Our focus in this study was to examine how Piteå-Tidningen produced Kaj Linna, the man who was accused and later convicted for murder. In addition to the frames we could distinguish about the perpetrator we also examined the small community, Kalamark, were the murder occured. In the next step of our analysis we examined how he was produced when he was declared innocent. We did this by applying a framing-analysis on 35 articles from Piteå-tidningen that covered the events that occured 2004 and 2017.   The frames we could identify from Piteå-Tidningen that described Kaj Linna 2004 was as an odd man, a man without no stable income and a man with money as his motivitaton. The community was framed as the victims, who stood together in sorrow and in despair. Kaj Linna got excluded and the community of Kalamark got included in the frames we identified.   The turning point in 2017, when Kaj Linna was declared innocent and was set to become a free man the frames changed. He was framed as a family man, a man with feelings that had people caring about him. Like a man who was one of us. He was included in 2017. The frames about the community in 2017 was hard to find as the focus of reporting about the case exclusively was about Kaj Linna.

Ce travail de thèse porte sur la chimie organométallique des complexes pince indényle/indénediide de palladium et de platine et leurs applications en catalyse coopérative métal-ligand. Le premier chapitre de ce manuscrit fait un point bibliographique non-exhaustif du domaine de la coopérativité métal-ligand, des travaux de Noyori sur l'hydrogénation asymétrique, jusqu'aux récents travaux de Milstein avec les ligands désaromatisés. Les ligands pince sont également présentés. Du premier exemple PCP décrit par Shaw jusqu'au CNC développé par Bezuidenhout. La versatilité de ces ligands est illustrée à travers quelques modifications permettant des réactivités originales ou l'isolation d'espèces hautement instables. Le second chapitre présente une nouvelle réaction de formation de cycle avec le complexe pince indénediide de palladium. Cette réaction implique pour la première fois deux molécules de substrat, le CO2 comme source C1 et les propargylamines/homopropargylamines. L'étude mécanistique du système a permis d'établir l'implication de la coopérativité métal-ligand. Ensuite, le troisième chapitre est un chapitre de chimie exploratoire. De nouvelles réactivités ont été étudiées avec les complexes pince de platine. L'activation de liaisons peu polaires telles que H-H et H-Si ont permis la réduction de liaisons insaturées. Les propositions mécanistiques, qu'il reste à confirmer, semblent indiquer que les métathèses ?, ainsi que les insertions migratoires, sont possibles avec ces complexes. Finalement, le dernier chapitre est consacré au développement d'un nouveau ligand pince ayant la particularité d'être hémilabile et ouvrant ainsi la voie à de nouvelles réactivités. Sa coordination au palladium, ainsi que la déprotonation de ce dernier, a permis le développement d'un complexe coopératif qui a été testé en cycloisomérisation. L'ensemble de ces travaux reflètent l'importance des ligands pince indényle/indénediide et de la coopérativité métal-ligand en catalyse. / This Ph.D. work deals with organometallic chemistry of indenyl/indenediide palladium and platinum pincer complexes and their applications in metal-ligand cooperative catalysis. The first chapter of this manuscript compiled a non-exhaustive bibliographic survey of the field of metal-ligand cooperation, from Noyori's system applied to the asymmetric hydrogenation, to the recent examples described by Milstein involving non-aromatic pincer ligands. Pincer ligands are also presented. Starting from the first example, in which Shaw shed light a PCP pincer, to the contemporary CNC pincer reported by Bezuidenhout. The versatility of those ligands is illustrated through few modulations allowing originals reactivities or stabilisation of highly unstable species. The second chapter is focused on the development of a new catalytic reaction with the indenediide palladium pincer complex. This reaction entail, for the first time, two substrates, the CO2 as a C1 source and propargylamines/homopropargylamines. The mechanistic studies turn out the importance of the metal-ligand cooperativity. Then, the third chapter concerns exploratory chemistry. New reactivities have been studied with the platinum complexes. The activation of low polar bond such as H-H and H-Si allowed the reduction of unsatured C-C bond. The mechanistic propositions, that remain to be confirmed, seem to indicate the feasibility of ? bond metathesis and migratory insertions. Finally, the last chapter is dedicated to the development of a new ligand. The latter showed the distinctive characteristic to be hemilabile, leading the way of new reactivities. His coordination to palladium, followed by his deprotonation to give rise to the non-innocent nature of the complex is presented, as well as the application of the resulting complex in the context of a cycloisomerisation. Those results are reflecting the importance of the indenyl and indenediide pincer ligands besides the metal-ligand cooperativity in catalysis.

La caractérisation complète d’intermédiaires réactionnels intervenants dans des procédés de catalyse homogène est une tâche ardue en raison de leur réactivité et de leur faible concentration. Ceci est particulièrement vrai pour les espèces radicalaires telles que les complexes organométalliques réduits, qui sont des intermédiaires en photocatalyse ou lorsque ces complexes possèdent des ligands non-innocents. Par conséquent, leur structure électronique est encore mal comprise, sachant que l'électron ajouté peut être situé sur différents sites de la molécule.Dans ce contexte, nous avons développé une méthode d'analyse pour étudier en phase gazeuse des complexes organométalliques radicalaires. Des complexes organométalliques multichargés du zinc et du ruthénium avec des ligands bidentes de type bipyridine ou tridente de type bis(imino)pyridine ont d’abord été obtenus et isolés en phase gazeuse. Ils sont ensuite réduits avec les méthodes d’activation par un électron spécifiques à la spectrométrie de masse, la dissociation par capture ou transfert d’électron (ECD/ETD), permettant de former des espèces métalliques radicalaires monochargées. Celles-ci sont enfin isolés et leur spectre infrarouge est obtenu à l’aide de la spectroscopie d’action basée sur la dissociation induite par l’absorption de plusieurs photons dans l’infrarouge (IRMPD). Les méthodes DFT fournissent un complément pour modéliser la structure électronique et le spectre IR de ces espèces.Les challenges à relever pour développer ce nouvel outil d'analyse étaient de deux ordres. Tout d'abord, nous devions être en mesure d'obtenir les complexes souhaités en phase gazeuse. Ceci nous a conduit à examiner de multiples paramètres, tels que la nature des ligands ou l’énergie interne déposée lors de l’étape de réduction. Le deuxième défi portait sur l'utilisation des méthodes de modélisation. Nous avons montré l’absence de fiabilité des méthodes standards de modélisation pour décrire à la fois la structure électronique et le spectre infrarouge des complexes réduits. Les données expérimentales obtenues durant ce travail ont donc été utilisées comme références pour identifier les fonctionnelles DFT les plus appropriées pour l’étude de ces complexes radicalaires. / The complete characterization of reaction intermediates in homogeneous catalytic processes is often a difficult task owing to their reactivity and low concentration. This is particularly true for radical species such as reduced organometallic complexes, which are intermediates in photocatalysis, or when these complexes included non-innocent ligands. Consequently, their electronic structure in the ground state is still poorly understood, knowing that the added electron can be located on different sites of the molecule.In this contect, we developed an analytical method to study radical organometallic complexes in the gas phase. We started with formation of suitable multi-charged zinc organometallic complexes in the gas phase from mixture of zinc metal cation and bipyridine-type bidentate or bis(imino)pyridine tridentate ligands. Multicharged ruthenium complexes with similar ligands have also been studied. Under ideal circumstances these complexes were isolated and reduced in the gas phase to form monocationic metal species. Electron activated methods such as electron capture dissociation (ECD) and electron transferred dissociation (ETD) techniques, available in FT-ICR mass spectrometers, have been used to that end. The resulting Zn and Ru radical cation complexes are then isolated in the gas phase and probed via infrared multi photon dissociation (IRMPD) action spectroscopy. In support, DFT theoretical calculations were performed to model their electronic structure and IR spectra.Two main issues were faced during the development of this new analytical tool. First, we had to be able to obtain the desired complexes in the gas phase. This has lead to monitor various parameters, such as the nature of the ligands or the internal energy provided by the reduction step. The second challenge dealt with the use of modeling methods. We have shown that standard modelling tools lack the accuracy to predict both electronic structure and spectral signatures of reduced complexes. The experimental data gathered in this work have therefore been used as benchmarks for the identification of DFT functionals that are most appropriate for the study of these radical complexes.

This study examines the figures of theיקדִּ צַ and עשָׁ רָ in psalms. Drawing on both semantics and poetics, this study argues that the contrast between the figures represented by these terms is part of the conventions of Hebrew psalmody and, as such, can serve various discursive functions within an individual psalm. Using insights from the field of lexical semantics, the study clarifies the possible uses of the words Justand עשָׁ רָ, emphasizing a wider range of uses than is typically offered within a broad behavioral domain for these terms. The study summarizes ways that various books in the Hebrew Bible use the contrast of these figures to develop a description of the literary features related to their presentations. The analysis of 18 psalms that include both figures utilizes insights from narratological theories of character to explore the functions of the contrast between קידִּ צַ and עשָׁ רָ as literary figures within the overall discourse of the psalm. Focusing on the setting of an individual psalm and embracing the possibility of variation reveals that קידִּ צַ and עשָׁ רָ are not only, or even usually, employed to describe the “prototypically good” or “prototypically bad” person in psalms. Rather, the עשָׁ רָ is often a designation for an antagonist, and the קידִּ צַ is often understood as one who is innocently wronged. As such, the literary pattern of their contrast does not focus on the moral character of these figures but on the fairness or justice of God to eventually elevate the position of the קידִּ צַ and destroy the עשָׁ רָ.

The struggle between church and state continued during the thirteenth century. The crusades continued in the East with the advance of Islam. Crusades were also called for to put an end to heresies, in particular the Albigensian heresy. Unfortunately the established orders, such as the Cistercians, failed to combat heresy and to solve the problems of corruption in the Church. Scholastic theology developed with the establishment of the universities. These events influenced the thirteenth century. During the thirteenth century spiritual renewal began with Pope Innocent III. Councils like the Fourth Lateran Council defined church teaching and addressed corruption of the clergy. However, one of the most important sources of spiritual renewal came from the mendicant orders who had been given permission by Pope Innocent III to operate in the Church. These orders contributed immensely to education in the universities and through the Catholic laity culture advanced. / Die stryd tussen kerk en staat het voortgegaan gedurende die dertiende eeu. Die kruistogte het voortgeduur in die Ooste met die aanruk van Islam. Kruistogte was ook aangeroep om sodoende ‘n einde te maak aan kettery, veral Albiganiese kettery. Ongelukkig die ontwikkelde heerskappye, soos die Cisteriaanse orde, het nie daarin geslaag om probleme soos kettery en korrupsie in die kerk op te los. Skolastiese teologie het ontwikkel met die vestiging van die universiteite. Hierdie gebeure het ‘n kardinale impak gehad op die dertiende eeu. Gedurende die periode, het geestelik hernuwing begin met Pous Innocent III. Owerhede soos die Vierde Laterniese Owerheid het godsdiens onderrig, gedefinieer en korrupsie aangespreek. Tog, was een van die belangrikste bronne van geestelike hernuwing, die Bedelmonnik Orde, wat toestemming van Pous Innocent III gekry het om in die kerk te handel. Hierdie orde het bygedra tot onderig in universiteite en deur Katoliek leke het kultuur voortgespruit. / Christian Spirituality, Church History & Missiology / M. Th. (Church History)

The struggle between church and state continued during the thirteenth century. The crusades continued in the East with the advance of Islam. Crusades were also called for to put an end to heresies, in particular the Albigensian heresy. Unfortunately the established orders, such as the Cistercians, failed to combat heresy and to solve the problems of corruption in the Church. Scholastic theology developed with the establishment of the universities. These events influenced the thirteenth century. During the thirteenth century spiritual renewal began with Pope Innocent III. Councils like the Fourth Lateran Council defined church teaching and addressed corruption of the clergy. However, one of the most important sources of spiritual renewal came from the mendicant orders who had been given permission by Pope Innocent III to operate in the Church. These orders contributed immensely to education in the universities and through the Catholic laity culture advanced. / Die stryd tussen kerk en staat het voortgegaan gedurende die dertiende eeu. Die kruistogte het voortgeduur in die Ooste met die aanruk van Islam. Kruistogte was ook aangeroep om sodoende ‘n einde te maak aan kettery, veral Albiganiese kettery. Ongelukkig die ontwikkelde heerskappye, soos die Cisteriaanse orde, het nie daarin geslaag om probleme soos kettery en korrupsie in die kerk op te los. Skolastiese teologie het ontwikkel met die vestiging van die universiteite. Hierdie gebeure het ‘n kardinale impak gehad op die dertiende eeu. Gedurende die periode, het geestelik hernuwing begin met Pous Innocent III. Owerhede soos die Vierde Laterniese Owerheid het godsdiens onderrig, gedefinieer en korrupsie aangespreek. Tog, was een van die belangrikste bronne van geestelike hernuwing, die Bedelmonnik Orde, wat toestemming van Pous Innocent III gekry het om in die kerk te handel. Hierdie orde het bygedra tot onderig in universiteite en deur Katoliek leke het kultuur voortgespruit. / Christian Spirituality, Church History and Missiology / M. Th. (Church History)