abstract: The search for highly active, inexpensive, and earth abundant replacements for existing transition metal catalysts is ongoing. Our group has utilized several redox non-innocent ligands that feature flexible arms with donor substituents. These ligands allow for coordinative flexibility about the metal centre, while the redox non-innocent core helps to overcome the one electron chemistry that is prevalent in first row transition metals. This dissertation focuses on the use of Ph2PPrDI, which can adopt a κ4-configuration when bound to a metal. One reaction that is industrially useful is hydrosilylation, which allows for the preparation of silicones that are useful in the lubrication, adhesive, and cosmetics industries. Typically, this reaction relies on highly active, platinum-based catalysts. However, the high cost of this metal has inspired the search for base metal replacements. In Chapter One, an overview of existing alkene and carbonyl hydrosilylation catalysts is presented. Chapter Two focuses on exploring the reactivity of (Ph2PPrDI)Ni towards carbonyl hydrosilylation, as well as the development of the 2nd generation catalysts, (iPr2PPrDI)Ni and (tBu2PPrDI)Ni. Chapter Three presents a new C-O bond hydrosilylation reaction for the formation of silyl esters. It was found the (Ph2PPrDI)Ni is the most active catalyst in the literature for this transformation, with turnover frequencies of up to 900 h-1. Chapter Four explores the activity and selectivity of (Ph2PPrDI)Ni for alkene hydrosilylation, including the first large scope of gem-olefins for a nickel-based catalyst. Chapter Five explores the chemistry of (Ph2PPrDI)CoH, first through electronic structure determinations and crystallography, followed by an investigation of its reactivity towards alkyne hydroboration and nitrile dihydroboration. (Ph2PPrDI)CoH is the first reported cobalt nitrile dihydroboration catalyst. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2018

Magistriniame darbe kalbama apie nekilnojamojo daikto išreikalavimą iš sąžiningo įgijėjo. Aptariamos sąžiningo įgijėjo ir nekilnojamojo daikto sampratos. Kalbant apie sąžiningo įgijėjo sampratą, išsamiau, remiantis tiek teisinės literatūros, tiek teisminės praktikos analize, aptariamas sąžiningumo vertinimas bei supratimas. Tai pat darbe paliečiamas sąžiningo įgijėjo ir savininko atribojimas. Nekilnojamojo daikto sąvoka, kaip nesukelianti didelių teisinių diskusijų išreikalavimo iš sąžiningo įgijėjo kontekste, aptariama tik trumpai. Daugiausia dėmesio šiame darbe skiriama situacijų, kada nekilnojamasis turtas gali būti išreikalautas iš sąžiningo įgijėjo, analizei. Plačiausiai iš jų aptariamos išreikalavimo galimybės, kai nekilnojamasis daiktas įgytas neatlygintinai, varžytinėse ar nusikaltimo (įvykdyto perleidžiant nekilnojamąjį daiktą asmens, nesančio savininku) pasekoje. Taip pat trumpai aptariamos ir kitos situacijos, kai nekilnojamasis daiktas, gali būti išreikalautas iš sąžiningo įgijėjo. Darbe aprašomi nekilnojamojo daikto išreikalavimo būdai ir pasekmės, daugiau dėmesio skiriant vindikacijai, trumpai aptariant restituciją (kaip galimą varžytinių negaliojimo pasekmę). Autorė taip pat pateikia naują požiūrį į nekilnojamojo daikto išreikalavimą ir jo pasekmes iš sąžiningo įgijėjo. Dėl darbo apimties reikalavimų, magistriniame darbe buvo išsamiausiai aptariamos tik Lietuvos nekilnojamojo daikto išreikalavimo praktinės bei teorinės problemos, nesigilinant į užsienio šalių... [toliau žr. visą tekstą] / Master work refers to exaction of the real estate property from innocent acquirer. The perceptions of the innocent purchaser and immovable object were discussed. Analyzing the concept of innocent purchaser in more detail and in accordance with both the legal literature and case law analysis, the evaluation of fairness and understanding were made. This work also touched a division between innocent purchaser and owner. The concept of real estate object as issue that do not create a major legal debates in the context of exaction from the innocent purchaser were discussed only briefly. This master work focuses on analysis of situations in which real estate property may be exacted from the innocent acquirer. The possibilities of exacting real estate property which acquired free of charge, during competitive bidding or in crime (if a transfer of real estate property were made by person other than the owner) were most widely discussed. The situations where the real estate property may be exacted from just acquirer are also briefly discussed. The master work describes the methods and consequences of exacting real estate property by putting more emphasis to vindication and briefly discussing restitution (as a possible consequence of invalid competitive bidding). The author also provides a new approach to the exaction of real estate property from a just acquirer and its consequences. On the scope of work requirements, the master work had comprehensively discussed only practical and... [to full text]

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abstract: The late first row transition metals, being inexpensive and environmentally benign, have become very attractive for sustainable catalyst development. However, to overcome the detrimental one electron redox processes exhibited by these metals, the employment of redox non-innocent chelates turned out to be very useful. The Trovitch group has designed a series of pentadentate bis(imino)pyridine ligands (pyridine diimine, PDI) that are capable of binding the metal center beyond their 3-N,N,N core and also possess coordination flexibility. My research is focused on developing PDI-supported manganese catalysts for organic transformations and renewable fuel production. The thesis presents synthesis and characterization of a family of low valent (PDI)Mn complexes. Detailed electronic structure evaluation from spectroscopic and crystallographic data revealed electron transfer from the reduced metal center to the accessible ligand orbitals. One particular (PDI)Mn variant, (5-Ph2PPrPDI)Mn has been found to be the most efficient carbonyl hydrosilylation catalyst reported till date, achieving a maximum turnover frequency of up to 4950 min-1. This observation demanded a thorough investigation of the operative mechanism. A series of controlled stoichiometric reactions, detailed kinetic analysis, and relevant intermediate isolation suggest a mechanism that involves oxidative addition, carbonyl insertion, and reductive elimination. Noticing such remarkable efficiency of the (PDI)Mn system, it has been tested for application in renewable fuel generation. A modest efficiency for H2 production at an apparent pH of 8.4 have been achieved using a cationic Mn complex, [(Ph2PPrPDI)Mn(CO)]Br. Although, a detailed mechanistic investigation remained challenging due to complex instability, a set of relevant Mn(-I) intermediates have been isolated and characterized thoroughly. The dissertation also includes synthesis, characterization, and electronic structure evaluation of a series of Triphos supported iron complexes. Using this pincer chelate and either 2,2’-bipyridine (bpy) or 1,3,5,7-cyclooctatetraene (COT), a set of electronically interesting complexes have been isolated. Detailed electronic structure investigation using spectroscopy, magnetometry, crystallography, and DFT calculations revealed redox non-innocent behavior in the Bpy and COT ligands. Additionally, CO binding to the (Triphos)Fe system followed by reaction with borohydride reagents allowed for the isolation of some catalytically relevant and reactive iron hydride complexes. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2016

Ce travail de thèse s’est intéressé au développement de complexes de métaux non-nobles portant des ligands non-innocents et leurs applications en catalyse comme alternatives efficaces aux complexes de métaux nobles dans un contexte de fortes préoccupations économiques et environnementales. Ainsi, nous avons synthétisé et caractérisé des complexes de fer et de nickel portant des ligands non-innocents, à l’aide de différentes techniques spectroscopiques. Ces ligands pourraient moduler la réactivité du métal et étendre ainsi le champ d’applications de ces métaux de transition. Dans le but de développer de nouvelles méthodes de synthèse en catalyse au fer, des complexes de ce dernier avec des ligands bis(imino)pyridines ont été évalués pour une réaction tandem d’activation/arylation d’arènes non activés. Des études mécanistiques préliminaires, basées sur des données spectroscopiques (RMN, IR in situ, RPE) et théoriques (DFT), ont permis de suggérer un mécanisme différent de ceux connus pour le fer dans la littérature et n’est pas compatible avec un mécanisme de substitution aromatique radicalaire (HAS). Nous nous sommes également intéressés à un autre domaine majeur en catalyse : les réactions de couplage croisés catalysées par des complexes de nickel portant des ligands redox non-innocents. Les défis actuels de la catalyse au nickel sont la réalisation de couplage croisés d’halogénures d’alkyle non activés et les mécanismes impliqués diffèrent généralement de ceux mis en jeu dans les réactions de couplage croisé pallado-catalysées. Les réactions de couplage croisé catalysées par des complexes de nickel portant des ligands redox non-innocents ont été étudiées afin de découvrir de nouvelles réactivités et d’avoir une meilleure compréhension des cycles catalytiques mis en jeu. / This PhD work has focused on the development of complexes of non-noble metals bearing non-innocent ligands and their catalytic applications as efficient alternatives to noble metal complexes, in the light of increasing concerns regarding cost and sustainability-related issues of noble metals. Towards this goal, we have developed and characterized complexes of non-noble metals (Fe, Ni) with non-innocent ligands using multiple spectroscopic techniques. This work was aimed at broadening the field of useful catalytic applications of these particular complexes. For our dedicated program in iron catalysis, a new method for tandem C–H activation/arylation of unactivated arenes catalyzed by iron complexes bearing redox-active bis(imino)pyridine ligands was developed. Preliminary mechanistic insights were gained based on combined spectroscopic data (NMR, in situ IR, EPR), reactivity studies as well as DFT calculations. The results obtained are clearly in favor of a mechanism distinct to that previously reported for iron-based catalytic systems and are not compatible with homolytic aromatic substitution (HAS). We have also focused on another challenging field in catalysis: cross-coupling reactions catalyzed by nickel as base metal, bearing redox non-innocent ligands. Several challenges in cross-coupling reactions remain among which coupling of non-activated alkyl halides. Mechanisms involving nickel catalysts often differ from those involved in palladium catalyzed cross-coupling reactions. The behavior of nickel complexes bearing redox non-innocent ligands was studied in order to unveil new reactivites and gain a better understanding of the catalytic cycles at stake.

Indirect perpetration Abstract The topic of this diploma thesis is the analysis of an institute of indirect perpetration, which is one of many possible ways of committing a crime. Its essence lies in using other person who cannot be liable for his/her actions, also called an innocent agent or instrumentality. Such a person is controlled by an indirect perpetrator in the backround who must have double intentions towards committing a crime and also an abuse of a person who for some reason will not be held criminally liable. The reasons for staying out of criminal liability are enumeratively listed in the Criminal Code and include the lack of age, insanity, mistake, emergency, necessity and other defenses, as well as the fact that the person acted with no culpability or at all. It also deals with a matter when the innocent agent acts with no mental state (or motive) sufficient for commision of the offense which is required for particular criminal act and in those cases his liability can be measured at least as negligence and does not exclude his liability for another offense. This institute sought its way into the Criminal Code for quite a long time, until the enaction in 2009. The new Criminal Code was considered a groundbreaking legal regulation. By that time, the institute of indirect perpetration was only...

The thesis presents firstly the political and historical situation in the Late Roman Empire in which the Church was granted liberty. Through the historical events is shown how the theological discussions were jointed and influenced by the contemporary political situation of the Empire. Secondly, the life of the Pope Innocent I before and during his pontificate is presented and Nachleben of Innocent as a saint man, the style of his letters is involved too. In the same chapter is his pontificate described and discussed through letters, which he sent to various groups of bishops. These are divided into the following groups: Eastern bishops, bishops in Europe, boshops of Africa and the letters as a support for his friend John Chrysostom. In all these fields Innocent treats self-confidently, with the authority of the Roman bishop, but the kinds of claims to his authority depends on geographical location in which the letters are sent. Alongside the contribution of the basic introduction to the letters of the Pope Innocent I this thesis also offers the short excursion to the philological analysis and the selected theological topics (especially liturgical) of his letters.

Les ligands phosphasalen développés au sein du laboratoire peuvent être considérés comme les analogues phosphorés des ligands salen dont ils diffèrent par la présence de groupements iminophosphorane à la place des imines. L’introduction de ces fonctions a d’importantes conséquences sur les propriétés de ces ligands, qui sont plus électrodonneurs et plus flexibles que les dérivés salen correspondants, capables de stabiliser des métaux à haut degré d’oxydation. Ces ligands ont également un caractère redox non-innocent, une propriété très étudiée de nos jours tant en chimie de coordination qu’en catalyse.Dans la cadre de cette thèse, différents ligands ont été synthétisés en modifiant les différents paramètres au sein du ligand : les substituants du cycle phenolate, MeO vs. tBu (PsalentBu et PsalenOMe); les substituants du phosphore, alkyl vs. aryl (iPrPsalen); et le lien entre les deux azotes, avec l’introduction de différentes o-phenylenediamines à la place d’ethylenediamine, qui donne les ligands Psalophen, PsalophenOMe2, PsalophenMe and PsalophenCF3.Les complexes neutres de cuivre et nickel, ainsi que les produits de mono-oxydation ont été synthétisés et caractérisés. Pour déterminer précisément la structure électronique des complexes différentes techniques ont été utilisés : des spectroscopies UV-visible, RMN et RPE, voltampérométrie cyclique, diffraction de rayons X, mesures magnétiques à l’état solide (SQUID), ainsi que des calculs DFT.De manière générale ces travaux montrent que les phosphasalen sont mieux à même de stabiliser la densité de spin sur le métal, donnant en certains cas des complexes à haute valence (NiIII, CuIII) encore rares dans la littérature. Dans certains cas les observations expérimentales et les calculs pointent vers un état fondamental multiconfigurationel. Contrairement aux ligands salen, les complexes portant un lien aromatique entre les deux azotes dimerisent lors de l’oxydation. Afin de contrôler la densité électronique sur ce cycle, une série des complexes à ligands phosphasalophen ont été également étudies.Une synthèse de complexes phosphasalen de manganèse(II) et (III) a été également réalisée. La stabilisation des complexes oxo ou nitrido, ainsi que la catalyse d’oxydation ont été envisagés avec ces complexes et des résultats prometteurs ont été obtenus. / Phosphasalen ligands developed in our laboratory can be considered as the phosphorous analogues of salen ligands where the imines have been substituted by iminophosphorane functions. The presence of the P-N bond makes these ligands more electro-donating and more flexible than salen analogues. They are able to stabilize high-valent metal complexes, as in the case of a Ni phosphasalen complex, which was characterized as a NiIII complex in solution and in solid state. This was never obtained before with salen-type ligands.Phosphasalen ligands, as the salen ones, can act as redox non-innocent ligands. Therefore, upon oxidation either the ligand or the metal center can be oxidized depending on the relative energy of metal and ligand orbitals. This behavior has been deeply investigated in coordination chemistry and in catalysis.In order to elucidate the factors that influence the oxidation locus different ligands have been synthetized modifiying the phenolate subtituents, MeO vs. tBu (PsalentBu and PsalenOMe); the phosphorous substituents, alkyl vs. aryl (iPrPsalen); and the linker between the two nitrogen atoms, ethylenediamine vs. phenylenediamine (Psalophen, PsalophenOMe2, PsalophenMe and PsalophenCF3).The neutral and one-electron oxidized copper and nickel complexes were synthetized and characterized. In order to determine the electronic structure of the complexes a combination of different characterization techniques were used: UV-vis, EPR and NMR spectroscopies, cyclic voltammetry, X-ray diffraction, magnetic measurements (SQUID), as well as theoretical calculations.In a general manner, phosphasalen ligands favor a metal center oxidation in a higher extent than salen derivatives, leading in some cases to high-valent metal complexes (NiIII, CuIII), remaining rare cases in the literature. For some complexes, experimental observations and theoretical calculations point to the presence of multiconfigurational ground states. Contrary to salen, complexes bearing an aromatic linker between the two nitrogen atoms dimerize upon oxidation. In order to tune the electronic density in the central ring, a series of phosphasalophen complexes displaying different substituents in the aromatic bridge, have been studied.Manganese (II) and (III) phosphasalen complexes has been also studied. The stabilization of oxo and nitride complexes as well as catalytic applications have been targeted for these complexes and encouraging results have been obtained.

This thesis describes the synthesis and characterisation of metal complexes that contain chemically reduced bipyridyl ligands. The crystal structures of twenty-six novel complexes are reported alongside detailed discussions on the electronic and spectroscopic effects and trends associated with the different oxidation states within these species. Chapter One introduces the isomers of bipyridine and their redox chemistry, the concept of non-innocent ligands and the spectroscopic techniques that are currently used in determining ligand oxidation states. Subsequently, examples of main group, transition metal, lanthanide and actinide species that contain or may contain reduced forms of the ligand are discussed. Chapter Two details the synthesis and structural characterisation of alkali metal salts of singly and doubly reduced forms of the three commercially available bipyridine isomers. The effects of this reduction are investigated with the aim of developing diagnostic fingerprints for each of the ligand oxidation states. Chapter Three discusses the synthesis of an homologous series of compounds of the form [M(2,2'-bipy)(mes)₂]^n– where M = Cr, Mn, Fe, Co, Ni and n = 0, 1. Trends in magnetism, bonding and electronic structure are investigated with reference to theoretical calculations and the diagnostic fingerprints identified in the previous chapter. Chapter Four describes the synthesis and characterisation of three compounds containing the isostructural motif [Zn₂(4,4'-bipy)(mes)₄]^n– where n = 0, 1, 2. Structural and spectroscopic changes are discussed and com- pared to theoretical calculations. Chapter Five contains descriptions of the spectroscopic techniques employed in the above research and synthesis routes to all compounds featured in this thesis.

Antalet organdonatorer i Sverige räcker inte för att täcka behovet för dem som är i behov av organtransplantation. För att kunna bli organdonator krävs att vården vet om den avlidnes vilja. Det säkraste sättet att meddela sin vilja är genom donationsregister. Denna uppsats beskriver en förregistrerad experimentell mellangruppstudie som undersökte om deltagarnas (N = 348) intention till att registrera sig som organdonator påverkas av att få information om en person som är i behov av ett organ, jämfört med statistisk information. Dessutom undersöktes om intentionen påverkas av om det identifierade offret framställs som oskyldig eller icke-oskyldig. Datainsamlingen skedde via pappersenkäter. De mått som användes för intention att registrera sig som organdonator var dels självskattad intention, dels ett beteendemått där deltagarna fick svara på om de ville ha mer information. Resultaten av analysen av datan visade varken stöd för att ett oskyldigt identifierat offer skulle påverka deltagare till högre intention, eller att ett icke-oskyldigt identifierat offer skulle påverka deltagare till lägre intention. Någon signifikant skillnad fanns inte mellan grupperna för något av måtten. Studien gjordes inom ett område som inte är välbeforskat och mer forskning behövs för att kunna dra säkra slutsatser av resultatet. / The number of organ donors in Sweden is not enough to support the demand for those in need of organ transplants. To be able to become an organ donor the health services needs to know the will of the deceased. The surest way to announce one's will is through a donation register. This essay describes a pre-registered experimental between-group study that examined whether the participants’ (N = 348) intention to register as an organ donor is affected by receiving information about a person who is in need of an organ, compared with statistical information. In addition, it was examined whether the intention is affected by whether the identified are presented as innocent or non-innocent. Data gathering was done via paper surveys. The measures used for intention to register as an organ donor were partly a self-assessed intention, and partly a behavioral measure where the participants were to answer if they wanted more information. The results of the analysis of data neither supported that presentation of an innocent identified victim would influence participants to higher intention, nor that a non-innocently identified victim would influence participants to lower intention. There was no significant difference between the groups for any of the measures. The study was conducted in a field that is not well researched. More research is needed to be able to draw any absolute conclusions from the results.