Chelation-enforced metal-arene interactions : insights into substrate binding and catalysis by late transition metal complexes

Understanding and catalyzing chemical reactions requiring multiple electron transfers is an endeavor relevant to many outstanding challenges in the field of chemistry. To study multi-electron reactions, a terphenyl diphosphine framework was designed to support one or more metals in multiple redox states via stabilizing interactions with the central arene of the terphenyl backbone. A variety of unusual compounds and reactions and their relevance toward prominent research efforts in chemistry are the subject of this dissertation.

Chapter 2 introduces the para-terphenyl diphosphine framework and its coordination chemistry with group 10 transition metal centers. Both mononuclear and dinuclear compounds are characterized. In many cases, the metal center(s) are stabilized by the terphenyl central arene. These metal–arene interactions are characterized both statically, in the solid state, and fluxionally, in solution. As a proof-of-principle, a dinickel framework is shown to span multiple redox states, showing that multielectron chemistry can be supported by the coordinatively flexible terphenyl diphosphine.

Chapter 3 presents reactivity of the terphenyl diphosphine when bound to a metal center. Because of the dearomatizing effect of the metal center, the central arene of the ligand is susceptible to reactions that do not normally affect arenes. In particular, Ni-to-arene H-transfer and arene dihydrogenation reactions are presented. Additionally, evidence for reversibility of the Ni-to-arene H-transfer is discussed.

Chapter 4 expands beyond the chelated metal-arene interactions of the previous chapters. A dipalladium(I) terphenyl diphosphine framework is used to bind a variety of exogenous organic ligands including arenes, dienes, heteroarenes, thioethers, and anionic ligands. The compounds are structurally characterized, and many ligands exhibit unprecedented bindng modes across two metal centers. The relative binding affinities are evaluated spectroscopically, and equilibrium binding constants for the examined ligands are determined to span over 13 orders of magnitude. As an application of this framework, mild hydrogenation conditions of bound thiophene are presented.

Chapter 5 studies nickel-mediated C–O bond cleavage of aryl alkyl ethers, a transformation with emerging applications in fields such as lignin biofuels and organic methodology. Other group members have shown the mechanism of C–O bond cleavage of an aryl methyl ether incorporated into a meta-terphenyl diphosphine framework to proceed through β-H elimination of an alkoxide. First, the electronic selectivity of the model system is examined computationally and compared with catalytic systems. The lessons learned from the model system are then applied to isotopic labeling studies for catalytic aryl alkyl ether cleavage under dihydrogen. Results from selective deuteration experiments and mass spectrometry draw a clear analogy between the mechanisms of the model and catalytic systems that does not require dihydrogen for C–O bond cleavage, although dihydrogen is proposed to play a role in catalyst activation and catalytic turnover.

Appendix A presents initial efforts toward heterodinuclear complexes as models for CO dehydrogenase and Fischer Tropsch chemistry. A catechol-incorporating terphenyl diphosphine is reported, and metal complexes thereof are discussed.

Appendix B highlights some structurally characterized terphenyl diphosphine complexes that either do not thematically belong in the research chapters or proved to be difficult to reproduce. These compounds show unusual coordination modes of the terphenyl diphosphine from which other researchers may glean insights.

Proton-Coupled Reduction of N2 Facilitated by Molecular Fe Complexes

The activation of Fe-coordinated N₂ via the formal addition of hydrogen atom equivalents is explored in this thesis. These reactions may occur in nitrogenase enzymes during the biological conversion of N₂ to NH₃. To understand these reactions, the N₂ reactivity of a series of molecular Fe(N₂) platforms is investigated. A trigonal pyramidal, carbon-ligated Fe^I complex was prepared that displays a similar geometry to that of the resting state 'belt' Fe atoms of nitrogenase. Upon reduction, this species was shown to coordinate N₂, concomitant with significant weakening of the C-Fe interaction. This hemilability of the axial ligand may play a critical role in mediating the interconversion of Fe(N_xH_y) species during N₂ conversion to NH₃. In fact, a trigonal pyramidal borane-ligated Fe complex was shown to catalyze this transformation, generating up to 8.49 equivalents of NH₃. To shed light on the mechanistic details of this reaction, protonation of a borane-ligated Fe(N₂) complex was investigated and found to give rise to a mixture of species that contains an iron hydrazido(2-) [Fe(NNH₂)] complex. The identification of this species is suggestive of an early N-N bond cleavage event en route to NH₃ production, but the highly-reactive nature of this complex frustrated direct attempts to probe this possibility. A structurally-analogous silyl-ligated Fe(N₂) complex was found to react productively with hydrogen atom equivalents, giving rise to an isolable Fe(NNH₂) species. Spectroscopic and crystallographic studies benefited from the enhanced stability of this complex relative to the borane analogue. One-electron reduction of this species initiates a spontaneous disproportionation reaction with an iron hydrazine [Fe(NH₂NH₂)] complex as the predominant reaction product. This transformation provides support for an Fe-mediated N₂ activation mechanism that proceeds via a late N-N bond cleavage. In hopes of gaining more fundamental insight into these reactions, a series of Fe(CN) complexes were prepared and reacted with hydrogen-atom equivalents. Significant quantities of CH₄ and NH₃ are generated in these reactions as a result of complete C-N bond activation. A series of Fe(CNH_x) were found to be exceptionally stable and may be intermediates in these reactions. The stability of these compounds permitted collection of thermodynamic parameters pertinent to the unique N-H bonds. This data is comparatively discussed with the theoretically-predicted data of the N₂-derived Fe(NNH_x) species. Exceptionally-weak N-H bond enthalpies are found for many of these compounds, and sheds light on their short-lived nature and tendency to evolve H₂. As a whole, these works both establish and provide a means to understand Fe-mediated N₂ activation via the addition of hydrogen atom equivalents.

Late Transition Metals Supported by Aryl Ethers and Phenoxides Bearing Pendant Phosphines: Mechanistic Insights Relevant to Ether C-O Bond Cleavage

Terphenyl diphosphines bearing pendant ethers were prepared to provide mechanistic insight into the mechanism of activation of aryl C–O bonds with Group 9 and Group 10 transition metals. Chapters 2 and 3 of this dissertation describe the reactivity of compounds supported by the model phosphine and extension of this chemistry to heterogenous C–O bond activation.

Chapter 2 describes the synthesis and reactivity of aryl-methyl and aryl-aryl model systems. The metallation of these compounds with Ni, Pd, Pt, Co, Rh, and Ir is described. Intramolecular bond activation pathways are described. In the case of the aryl-methyl ether, aryl C–O bond activation was observed only for Ni, Rh, and Ir.

Chapter 3 outlines the reactivity of heterogenous Rh and Ir catalysts for aryl ether C–O bond cleavage. Using Rh/C and an organometallic Ir precursor, aryl ethers were treated with H2 and heat to afford products of hydrogenolysis and hydrogenation. Conditions were modified to optimize the yield of hydrogenolysis product. Hydrogenation could not be fully suppressed in these systems.

Appendix A describes initial investigations of bisphenoxyiminoquinoline dichromium compounds for selective C2H4 oligomerization to afford α-olefins. The synthesis of monometallic and bimetallic Cr complexes is described. These compounds are compared to literature examples and found to be less active and non-selective for production of α-olefins.

Appendix B describes the coordination chemistry of terphenyl diphosphines, terphenyl bisphosphinophenols, and biphenyl phosphinophenols proligands with molybdenum, cobalt, and nickel. Since their synthesis, terphenyl diphosphine molybdenum compounds have been reported to be good catalysts for the dehydrogenation of ammonia borane. Biphenyl phosphinophenols are demonstrated provide both phosphine and arene donors to transition metals while maintaining a sterically accessible coordination sphere. Such ligands may be promising in the context of the activation of other small molecules.

Appendix C contains relevant NMR spectra for the compounds presented in the preceding sections.

A bibliography of works for the identification of freshwater invertebrates in the British Isles

This bibliography covers the literature up to the end of 1978. The criteria used in the selection of references were that they should aid identification of invertebrates directly; thus, works solely concerned with the taxonomy of a particular group are in general omitted unless they contain a key. Some check-lists are however included where they give current nomenclature. The references are arranged alphabetically within each group and deal mainly with macro-invertebrates but include available keys to some microscopic invertebrates. Internal parasites and hymenopterous parasitoids are omitted. For insects the life stages to which the key applies are given where this is not clear in the reference. A number of keys to non-aquatic stages have been included in the hope that they may prove useful in certain circumstances. In addition, under a general head, latest check-lists are referred to together with bibliographies of algal keys and a guide for the identification of British water plants.

SNPs in microRNAs and susceptibility to Late-Onset Alzheimer´s disease

Case-control association study of SNPs in microRNAs and susceptibility to Late-Onset Alzheimer´s disease.

Osteometric analysis of the scapula and humerus of Rangifer tarandus and Cervus elaphus : A contribution to the discrimination of Late Pleistocene cervids

Fossil remains of reindeer (Rangifer tarandus) occurring outside their present range are an important indicator of formerly cold climatic conditions, but are easily confused with those of the red deer (Cervus elaphus). The locality of Kiputz IX has yielded one of the best-preserved Late Pleistocene reindeer populations of the southern Pyrenees, occurring in association with Bison priscus and the much more abundant Cervus elaphus. Fossil remains from this site are mostly complete and not affected by human intervention, thus creating the perfect conditions for reliable osteometric analyses. Here, we quantify diagnostic morphological features of the scapula and the humerus of Cervus elaphus and Rangifer tarandus to establish the potential of these bones to aid in interspecific discrimination. In the case of the scapula, the best species discriminator is the ratio of the minimum anteroposterior diameter of the scapular neck and the development of the articular process, while the breadth of the trochlea is the best discriminator in the case of the humerus.

Autobiografia de ficção como matéria de historicidade em João do Rio e em João Gilberto Noll

A análise de arquivos jornalísticos para a formação do conceito de historicidade em torno das obras Memórias de um rato de hotel (1912), de João do Rio, e Bandoleiros (1985), de João Gilberto Noll, foi a nossa primeira contribuição para a formação do objeto autobiografia de ficção, ou autoficção, como também denominamos. A partir desses arquivos de memórias, relativos a dois contextos finisseculares, o XIX e o XX respectivamente, pudemos compreender a historicidade como matriz do nosso objeto autoficção, permeada pelo que Foucault chama de efetividade cotidiana. Essa efetividade do cotidiano é costurada pelo fio da oralidade, que se refere ao elenco das atividades humanas no todo social, tendo como principal característica a ação comunicativa entre os sujeitos. Assim, ligamos a oralidade à historicidade em duas perspectivas complementares: os ditos e os escritos. A primeira diz respeito aos processos da comunicação humana e suas trocas simbólicas, que são projetadas na cultura: os ditos. A segunda se refere ao produto das representações literais do sujeito, grafadas no dorso impresso da memória: os escritos. A memória é a chave de acesso à escrita do si, que se distingue do que chamamos de autoficção, porque nessa última prevalecem as experiências do tempo presente para o futuro. Memórias de um rato de hotel é a escrita de um Eu-autor, contando do cárcere as suas experiências de gatuno no contexto da belle époque carioca. Por meio da memória, ele reconstrói o contexto finissecular, enfatizando a degradação urbana e a decadência ética da burguesia em ascensão, nos tempos da recém-inaugurada República. Na autoficção Bandoleiros, temos o relato vertiginoso de um Eu-narrador, contando do seus fracassos literários e conjugais. Ele é um escritor decadente, transitando nos espaços degradados da pós-modernidade, retirando dessa perambulação o material vivo de seu livro Sol macabro. Nessa autoficção, Noll registra as impressões sobre a realidade dos 1980, focalizando as subjetividades agônicas à margem do capitalismo tardio, num trânsito indômito entre Porto Alegre, Rio de Janeiro e os Estados Unidos. Na nossa tese, compreendemos a realidade como a matéria plástica da autobiografia de ficção. A experiência mundana do escritor é também forte aliada na composição de uma estética subjetiva, ou subjestética, que está para além do auto-retrato narcísico da autobiografia, em suas formas tradicionais

Retratos de Machado de Assis : sabedoria, genialidade e melancolia na crítica literária fin de siècle

Este ensaio de pensamento social brasileiro tem por objeto de análise as críticas literárias sobre a obra de Machado de Assis, publicadas em jornais e revistas imediatamente após o lançamento de cada um de seus livros. Portanto, são publicações de critica literárias escritas por contemporâneos do próprio Machado de Assis, e que, ao resenharem suas obras evidenciam o cenário e os modelos de interação vivenciados pelos artistas e intelectuais do período. Assim como expõem ainda as compreensões de literatura e de artista que fazem parte de seus repertórios analíticos. Este ensaio busca identificar, através das categorias mobilizadas para retratar Machado de Assis, as transformações ocorridas nestes modelos de interação social do período, e como a sociabilidade intelectual e artística, inicialmente vinculada ao padrão de gosto cortesão estabelecido no Rio de Janeiro, foi cedendo espaço para outros modelos de interação, e assim permitiu o desenvolvimento de diferentes compreensões de literatura e do papel da crítica literária, contribuindo diretamente para a alteração nos discursos retóricos das resenhas literárias. Portanto, este ensaio tenta identificar e entender os modelos retóricos inscritos na crítica, e como estes discursos estão correlacionados à transformações de ordem mais profunda, principalmente com o processo de modernização social e a construção da autonomia do universo intelectual e artístico no fim do século XIX e na primeira década do século XX

The all-seeing mirror: reflecting on vampires as allegories in socio-culturally sensitive literary works

Esta dissertação tem como objetivo analisar a figura do vampiro na literatura como poderosa ferramenta de leitura e interpretação dos medos e angústias que afligem um determinado espaço sociocultural. Ao olhar para a evolução do vampiro literário através dos séculos dezenove, vinte e vinte e um, notamos que cada uma de suas encarnações difere dramaticamente da anterior, e no que o vampiro é reinventado, ele engaja-se num diálogo pertinente e coerente com questões de seu próprio tempo, nunca perdendo assim sua relevância. Sua existência heterogênea, explicitada na dissertação primariamente através das obras Carmilla, de Sheridan LeFanu, Dracula, de Bram Stoker, Eu Sou a Lenda, de Richard Matheson, Entrevista com o Vampiro, de Anne Rice e Fledgling, de Octavia Butler, e as diferentes questões suscitadas em cada uma dessas obras como a sexualidade, a alteridade e o hibridismo nos levarão ao entendimento de que o vampiro pode potencialmente desempenhar importante função alegórica, tornando-se um espelho da própria humanidade através da qual se sustenta

O cantar da Germânia: política e cultura na Alemanha na passagem dos séculos XII e XIII

Esta tese desenvolvida na linha de pesquisa Política e Cultura destaca o interesse pelos fenômenos da transmissão do conhecimento intelectual. A tese reconstrói a expressão da cultura política medieval germânica pela ótica de dois poetas, Walther von der Vogelweide e Wolfram von Eschenbach, integrantes da aristocracia guerreira. Os suportes teóricos dos Sprüche, sentenças de natureza política de Vogelweide e do Parzifal de Eschenbach, foram fundamentais para compreender o posicionamento político e cultural alemão frente às transformações que afetaram a Cristandade no período de fins do século XII ao início do século XIII. Esse período foi marcado pelo confronto de Papas e Imperadores em torno do direito de exercer a autoridade no âmbito do Sacro Império Romano-Germânico. O movimento cruzadista, o renascimento urbano e a ascensão de novos atores sociais burgueses integram o conjunto dos elementos a serem levados em conta na elaboração da tese. A ideia norteadora do trabalho tornou necessário recorrer a obras literárias com objetivo de elucidar questões de natureza histórica, tendo claro que a Literatura não é um contraponto da História e o texto resultante contribua para ressignificar a produção política da cultura medieval e um melhor entendimento dos mecanismos do poder na Alemanha medieval. No plano teórico-metodológico recorremos à chamada História Cultural fornecendo uma visão integradora dos planos político, social e econômico.

Island life in the Cretaceous - faunal composition, biogeography, evolution, and extinction of land-living vertebrates on the Late Cretaceous European archipelago

The Late Cretaceous was a time of tremendous global change, as the final stages of the Age of Dinosaurs were shaped by climate and sea level fluctuations and witness to marked paleogeographic and faunal changes, before the end-Cretaceous bolide impact. The terrestrial fossil record of Late Cretaceous Europe is becoming increasingly better understood, based largely on intensive fieldwork over the past two decades, promising new insights into latest Cretaceous faunal evolution. We review the terrestrial Late Cretaceous record from Europe and discuss its importance for understanding the paleogeography, ecology, evolution, and extinction of land-dwelling vertebrates. We review the major Late Cretaceous faunas from Austria, Hungary, France, Spain, Portugal, and Romania, as well as more fragmentary records from elsewhere in Europe. We discuss the paleogeographic background and history of assembly of these faunas, and argue that they are comprised of an endemic 'core' supplemented with various immigration waves. These faunas lived on an island archipelago, and we describe how this insular setting led to ecological peculiarities such as low diversity, a preponderance of primitive taxa, and marked changes in morphology (particularly body size dwarfing). We conclude by discussing the importance of the European record in understanding the end-Cretaceous extinction and show that there is no clear evidence that dinosaurs or other groups were undergoing long-term declines in Europe prior to the bolide impact.

Creating dangerously: literature as an instrument of resistance in the works of Edwidge Danticat

O objetivo desta dissertação é discutir o lugar que o fazer literário ocupa no processo de resistência à poderes hegemônicos. Como fontes primárias centrais, foram escolhidos o romance histórico The Farming of Bones (1998) e a narrativa autobiográfica Brother, Im Dying (2007), ambos escritos pela autora haitiana-americana Edwidge Danticat. Em The Farming of Bones, Danticat reconstrói ficcionalmente o trágico e obscuro episódio ocorrido em 1937 quando o então ditador da República Dominicana, Rafael Trujillo, ordenou o extermínio de todos os haitianos que residiam e trabalhavam em cidades dominicanas próximas à fronteira com o Haiti. O silêncio por parte dos governos de ambos os países em torno do massacre ainda perdura. A publicação do romance histórico de Danticat 61 anos após tal ato de terrorismo de Estado se torna, desta forma, exemplo de como o fazer literário e o fazer histórico podem fundir-se. Em Brother, Im Dying, Danticat narra a história da vida e da morte de suas duas figuras paternas, seu pai Andre (Mira) Dantica e seu tio Joseph Dantica (que a criou dos 4 aos 12 anos, no Haiti). Joseph, sobrevivente de um câncer de laringe, foi pastor batista e fundador de uma igreja e uma escola no Haiti. Morreu dois dias depois de pedir asilo político nos EUA e ser detido na prisão Krome, em Miami. Mira, que migrara no início da ditadura de François Duvalier para os EUA, onde trabalhou como taxista, morreu vítima de fibrose pulmonar poucos meses depois de seu irmão mais velho. Edwidge Danticat recebeu a notícia de que o quadro de seu pai era irreversível no mesmo dia em que descobriu que está grávida de sua primeira filha. Com uma escrita que abrange tanto a narrativa de si quanto a narrativa do outro, além das esferas públicas e privadas, Danticat cria em Brother, Im Dying um locus de fazer auto/biográfico que dialoga com questões de diáspora, identidade cultural e memória. Os ensaios publicados em Create Dangerously (2010) e as várias entrevistas concedidas por Danticat também reforçam meu argumento que Edwidge Danticat exerce seu papel de artista engajada através de seu fazer principalmente, mas não exclusivamente literário. Desta forma, a autora constrói uma possibilidade de resistência ao discurso hegemônico que opera tanto em seu país de origem quanto em seu país de residência.

An investigation into the potential losses of fish on the filter plates at the Hodder Water Treatment Works Stocks Reservoir

Stocks Reservoir is situated amidst the Forest of Bowland in the upper reaches of the old river valley of the Hodder. The reservoir was built in 1927 for the Fylde Water Board who primarily supplied water to Blackpool. The objective of this study is to assess the degree and likelihood of fish ingress onto the fish plates at the present and proposed stocking densities. An additional aim is to evaluate the operational implications, and if necessary suggest methods of alleviating the problem. Three spheres of study have been undertaken to achieve these objectives, these being: 1. To selectively stock the reservoir and monitor the angling club catches in order to assess the total population, relating it to fish plate losses and proposed stocking densities. 2. To monitor the fish taken from the fish plates and assess the reasons for their ingress. 3. To study the draw off tower and fish plates, and suggest ways of ameliorating or halting the loss of fish and consequent operational problems.

The effect of organotin and copper sulfate on the late development and presettlement behavior of the hard clam Mercenaria mercenaria

The effect of organotin compounds and copper, commonly used as antifouling agent, were studied on Mercenaria mercernaria larvae. They were reared under usual hatchery conditions until they reached 190 um in diameter. The larvae were subjected to four compounds, tributylin chloride (TBT), monobutyltin chloride (MBT), trimethyltin chloride (TMT), cupric sulfate (CuSo4) plus control. Mortality was measured at 24, 48 h, and 96h. Behavioral and/or metamorphic changes were recorded in triplicate at 24-48 and 96 h. The appearance in swimming larvae of a functional foot was considered a sign of competence to set and was recorded as a "pediveliger". Swimming larvae were considered as larvae that have not yet reached their total development and they were recorded as "swimming". Larvae that did not show foot or swimming activity and were static but alive on the bottom were recorded as "bottom". TBT was found to completely inhibit swimming activity at sublethal concentrations throughout the period of observation. Copper and MBT inhibited swimming from 48 h, TMT did not inhibit swimming activity at any of the times recorded. The four compounds ranked in order of decreasing toxicity were TBT>TMT>CU>MBT.

The Many Lovers of Jane Austen: Irony & Parody

Master in Literature and Literary Science