abstract: This dissertation develops a second order accurate approximation to the magnetic resonance (MR) signal model used in the PARSE (Parameter Assessment by Retrieval from Single Encoding) method to recover information about the reciprocal of the spin-spin relaxation time function (R2*) and frequency offset function (w) in addition to the typical steady-state transverse magnetization (M) from single-shot magnetic resonance imaging (MRI) scans. Sparse regularization on an approximation to the edge map is used to solve the associated inverse problem. Several studies are carried out for both one- and two-dimensional test problems, including comparisons to the first order approximation method, as well as the first order approximation method with joint sparsity across multiple time windows enforced. The second order accurate model provides increased accuracy while reducing the amount of data required to reconstruct an image when compared to piecewise constant in time models. A key component of the proposed technique is the use of fast transforms for the forward evaluation. It is determined that the second order model is capable of providing accurate single-shot MRI reconstructions, but requires an adequate coverage of k-space to do so. Alternative data sampling schemes are investigated in an attempt to improve reconstruction with single-shot data, as current trajectories do not provide ideal k-space coverage for the proposed method. / Dissertation/Thesis / Doctoral Dissertation Mathematics 2019

Aim: The aim of the study was to compile scientific studies that studied the reliability of the caries risk assessment instruments (CAMBRA, Cariogram and R2) and their capacity to predict future caries development in children and adolescents. Method: The study is a general literature study based on scientific articles obtained from the databases Dentistry & Oral Sciences source (DOSS), PUBMED, CINAHL, SwePub and SveMed+. The articles were selected according to inclusion-/exclusion criteria. The included studies were reviewed with modified review template to present studies of strong value. The result is based on a total of 17 scientific articles that respond to the study's purpose and questions. Result: Caries risk assessment instrument is a useful tool in dental care, as it facilitates work with the risk grouping of patients. However, there is a need for further development of the various instruments in order for these to be considered fully reliable. Conclusion: The common feature of the three caries risk assessment instruments is that these should be reviewed and further developed in order to achieve full reliability. / Syfte: Syftet med litteraturstudien var att sammanställa vetenskapliga studier som studerat tillförlitligheten av kariesriskbedömningsinstrumenten (CAMBRA, Cariogram och R2) och deras kapacitet att förutse framtida kariesutveckling hos barn och ungdomar. Metod: Studien är en allmän litteraturstudie baserad på vetenskapliga artiklar hämtade från databaserna Dentistry & Oral Sciences source (DOSS), PUBMED, CINAHL, SwePub och SveMed+. Artiklarna har valts ut med hjälp av inklusion- och exklutionskriterier. De inkluderade artiklarna granskades med hjälp av en modifierad kvalitetsgranskningsmall för att fastställa att studierna vara av hög validitet, reliabilitet och kvalitet. Resultatet baseras på totalt 17 vetenskapliga artiklar som svarar på studiens syfte och frågeställning. Resultat: Användning av de tre kariesriskbedömningsinstrumenten är ett bra hjälpmedel inom tandvården, då det underlättar vid riskgruppering av patienter. Dock finns ett stort behov av vidareutveckling av de olika instrumenten för att dessa ska anses fullt tillförlitliga. Slutsats: Gemensamt för de tre kariesriskbedömningsinstrumenten är att dessa bör granskas och vidareutvecklas för att full tillförlitlighet ska kunna uppnås.

A Regressão Robusta surge como uma alternativa ao ajuste por mínimos quadrados quando os erros são contaminados por pontos aberrantes ou existe alguma evidência de violação das suposições do modelo. Na regressão clássica existem critérios de seleção de modelos e medidas de diagnóstico que são muito conhecidos. O objetivo deste trabalho é apresentar os principais critérios robustos de seleção de modelos e medidas de detecção de pontos aberrantes, assim como analisar e comparar o desempenho destes de acordo com diferentes cenários para determinar quais deles se ajustam melhor a determinadas situações. Os critérios de validação cruzada usando simulações de Monte Carlo e o Critério de Informação Bayesiano são conhecidos por desenvolver-se de forma adequada na identificação de modelos. Na dissertação confirmou-se este fato e além disso, suas alternativas robustas também destacam-se neste aspecto. A análise de resíduos constitui uma forte ferramenta da análise diagnóstico de um modelo, no trabalho detectou-se que a análise clássica de resíduos sobre o ajuste do modelo de regressão linear robusta, assim como a análise das ponderações das observações, são medidas de detecção de pontos aberrantes eficientes. Foram aplicados os critérios e medidas analisados ao conjunto de dados obtido da Estação Meteorológica do Instituto de Astronomia, Geofísica e Ciências Atmosféricas da Universidade de São Paulo para detectar quais variáveis meteorológicas influem na temperatura mínima diária durante o ano completo, e ajustou-se um modelo que permite identificar os dias associados à entrada de sistemas frontais. / Robust Regression arises as an alternative to least squares method when errors are contaminated by outliers points or there are some evidence of violation of model assumptions. In classical regression there are several criteria for model selection and diagnostic measures that are well known. The objective of this work is to present the main robust criteria of model selection and outliers detection measures, as well as to analyze and compare their performance according to different stages to determine which of them fit better in certain situations. The cross-validation criteria using Monte Carlo simulations and Beyesian Information Criterion are known to be adequately developed in model identification. This fact was confirmed, and in addition, its robust alternatives also stand out in this aspect. The residual analysis is a strong tool for model diagnostic analysis, in this work it was detected that the classic residual analysis on the robust linear model regression fit, as well as the analysis of the observations weights, are efficient measures of outliers detection points. The analyzed criteria and measures were applied to the data set obtained from the Meteorological Station of the Astronomy, Geophysics and Atmospheric Sciences Institute of São Paulo University to detect which meteorological variables influence the daily minimum temperature during the whole year, and was fitted a model that allows identify the days associated with the entry of frontal systems.

Made available in DSpace on 2015-08-19T13:52:53Z (GMT). No. of bitstreams: 2 4.pdf: 437106 bytes, checksum: d927c757f12edab980517854aaef9262 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2012 / Fundação Oswaldo Cruz. Instituto de Tecnologia em Fármacos/Farmanguinhos. Rio de Janeiro, RJ, Brasil. / Esta dissertação avalia o impacto da aplicação do princípio de Quality by Design(QbD) apresentado no Guia ICH Q8(R2) Desenvolvimento Farmacêutico sobre a qualidade do processo de desenvolvimento e de produção de novos medicamentos de Farmanguinhos.O objetivo do desenvolvimento farmacêutico é projetar um produto de qualidade cujo processo de fabricação permita, de forma consistente, alcançar o desempenho pretendido com reprodutibilidade e confiabilidade. As informações e os conhecimentos adquiridos a partir de estudos de desenvolvimento farmacêutico e da experiência de fabricação podem servir de base para o gerenciamento de riscos de qualidade, bem como fornecem uma compreensão científica para subsidiar a definição do espaço do projeto, das especificações e dos controles de fabricação. As recomendações do Guia ICH Q8(R2) permitem sistematizar o conhecimento adquirido a partir da aplicação de métodos científicos e do gerenciamento de risco ao desenvolvimento de um produto e seu processo de fabricação. A compreensão dos fatores associados ao desempenho do produto, que deve ser demonstrada pela empresa a fim de embasar e viabilizar a flexibilização dos critérios regulatórios, pode ser adquirida pela aplicação da Tecnologia Analítica de Processo (PAT). O guia da Food and Drug Administration(FDA) referente à PAT destina-se a apoiar a inovação e a eficiência no desenvolvimento, fabricação e garantia de qualidade de produtos farmacêuticos. Sua estrutura é baseada na compreensão do processo para facilitar a inovação e as decisões regulatórias da indústria e da autoridade sanitária. A indústria farmacêutica brasileira vem se esforçando para estabelecer sistemas de qualidade robustos, baseados em conhecimentos científicos e nos princípios da análise e gerenciamento de riscos. Para Farmanguinhos , a implantação do Guia ICH Q8(R2) poderá trazer diversos benefícios, incluindo a melhoria na eficiência do processo de desenvolvimento e um significativo ganho de qualidade, com minimização dos riscos. Além disso, proporcionará uma estratégia para aumentar o conhecimento e a compreensão de seus produtos e processos de fabricação, e introduzirá práticas e conceitos oriundos da normatização global mais recente, facilitando a consolidação do Instituto como centro de referência em pesquisa, desenvolviment o tecnológico e produção de fármacos e medicamentos. Pela avaliação feita, apesar do processo de desenvolvimento farmacêutico de Farmanguinhos se encontrar num nível de maturidade inicial, há um esforço da equipe técnica multidisciplinar em buscar a aderência de suas atividades e da estrutura de documentação às diretrizes do Guia ICH Q8(R2). É apresentada uma proposta de procedimento para utilização dos princípios do QbD e da PAT no Instituto, a qual, se introduzida, em alguma extensão, na rotina de trabalho da Unidade, trará um ganho tecnológico e de qualidade, bem como um incremento na celeridade de possíveis alterações pós-registro que se façam necessárias no futuro. / This work evaluates the impact of the app lication of the principle of Quality by Design (QbD) presented in the ICH Guideline Q8(R2) "Pharmaceutical Development" on the quality of the development process and prod uction of new drugs of Farmanguinhos. The goal of pharmaceutical development is designing a quality product whose manufacturing process to consistently achieve the desired performance with reproducibility and reliability. The information and knowledge gained from studies of pharmaceutical development and manufacturing experience can serve as a basis for the risk management of quality, as well as provide a scientific understanding to subsidize the design space definition, specifications and manufacturing controls. The recommendations of the ICH Guideline Q8(R2) enable to systematize the knowledge acquired from the application of scientific methods and risk management to the development of a product and its manufacturing process. Understanding of the factors associated with the performance of the product, which must be demonstrated by the company in order to support and enable flexible regulatory criteria, can be acquired by application of Pr ocess Analytical Technology (PAT). The Food and Drug Administration (FDA) guideline for th e PAT is intended to support innovation and efficiency in the development, manufacturi ng and quality assurance of pharmaceuticals. Its structure is based on the understanding of the process in order to facilitate innovation and industry regulatory decisions and health authority. The Brazilian pharmaceutical industry has been trying hard to establish robust quality systems, based on scientific knowledge and the pr inciples of risk analysis and management. For Farmanguinhos, implementation of ICH Q8(R2) can bring several benefits, including improving the efficiency of the development process and a significant gain in quality, with minimization of risks. In addition, it will provide a strategy to increase the knowledge and understanding of their products and manufacturing processes, and introduce practices and concepts from the latest global standardization, facilitating the consolidation of the Institute as the center of reference in research, technological development and production of drugs and medicines. An evaluation was made, and it was possible conclude there is a multidisciplinary technical team effort in seeking the grip of its activities and structure documentation guide ICH Guidelines Q8(R2), despite the pharmaceutical development process of Farmanguinhos is in initial maturity level. A procedural proposal for use of QbD and PAT principles at the Institute is presented. If it is introduced, in some extent, in the routine work of the Unit, it will bring a technological and quality gain, as well as an increase in the speed of possible post-registration changes that may be required in the future.

Uppsatsen undersöker om valet av hanteringsmetod av ordinalskalevariabler kan kopplas till den linjära regressionsmodellens prediceringsförmåga. Antalet hanteringsmetoder som undersöks begränsas till: dummyvariabler, summerat index och viktat summerat index. Stöd för alla tre metoder finns i litteraturen även om det för indexeringarna finns viss förvirring i begreppsanvändning. Med summerat index menas, i denna uppsats, när flera indikatorer som mätts med likertskalor adderas till en ny variabel som antas mäta den latenta variabeln. Med viktat summerat index tas det hänsyn till att indikatorerna kan vara något överlappande eller ha olika stor betydelse för den latenta variabeln. Därför appliceras någon form av viktningsanalys på indikatorerna innan summering sker, denna uppsats använder principalkomponentsanalys. K-delad korsvalidering har nyttjats som främsta analysverktyg för att kunna jämföra de olika hanteringsmetoderna. Jämförandet sker på basis av fyra jämförande mått: R2 , Steins  R2j , RMSE samt MAE. Resultaten indikerar att modeller med dummyvariabler har bäst prediceringsförmåga men det ska förstås utifrån att modellerna hade problem med att uppfylla den linjära regressionsmetodens antaganden. Alla tre hanteringsmetoder har sina för- och nackdelar och därför behöver valet av hanteringsmetod alltid ske med hänsyn till aktuell undersökning.

Stem diameter at breast height (D1.3m) and tree height (H) are commonly used measures of tree growth. Based on correlation analysis between biomass of stem, branches and leaves and stem diameter and height of tree we can identify allometric equation for predicting biomass and carbon sequestration of the vegetation. This study was carried out in the natural forests of Me Linh Station for biodiversity to develop allometric equation between biomass and diameter at breast height and height of tree. The study results indicated that twenty tree species dominate in natural forests in Me Linh Station for Biodiversity and they were selected for sampling. Through the 80 established linear equation models for above and below –ground biomass (AGB and BGB), we found that the biomass of tree species in Me Linh Station for Biodiversity were closely correlated with the diameter factor (R>0.902) and not clearly correlated with the height (correlation coefficient = 0.5498, R2< 0.549). Four regression equations were established, including: Pstem = 25.3051*(D1.3m)0.4627 (R2 : 9.661); Pbranch = 12.1043*( D1.3m)0.5416 (R2 : 9.8); Pleaves = 9.446*(D1.3m)0.5976 (R2 : 0.9363); P total biomass of forest = 25.882*D1.725 with R2: 0.8561) for estimating biomass and carbon sequestration of natural forest at the research site. / Đường kính ngang ngực (D1.3m) và chiều cao (H) cây là hai nhân tố thường được dùng để đánh giá sự phát triển của cây gỗ. Việc xây dựng các phương trình tương quan giữa sinh khối (SK) thân, cành, lá, sinh khối tầng cây gỗ, sinh khối của quần xã thực vật với đường kính và chiều cao cây góp phần rất lớn trong dự báo sinh khối và khả năng hấp thụ khí carbon của thảm thực vật. Kết quả nghiên cứu cho thấy 20 loài cây gỗ chiếm ưu thế trong rừng tự nhiên và chúng được chọn để thu mẫu. Mối tương quan giữa sinh khối với 2 nhân tố điều tra rừng là đường kính ngang ngực và chiều cao cây đã đươc kiểm tra thông qua 80 phương trình tương quan. Nhìn chung, sinh khối có tương quan chặt chẽ với nhân tố đường kính (hệ số tương quan R > 0,902), và không tương quan rõ với nhân tố chiều cao (R < 0,5498). Bốn phương trình tính sinh khối cho thảm rừng tại khu vực nghiên cứu đã được thiết lập: SKthân = 25,3051*(D1,3m)0,4627 (R2: 9,661); SKcành: 12,1043*(D1,3m)0,5416 (R2: 9,8); SKlá: 9,446*(D1,3m)0,5976 (R2: 0,9363) và SKtổng = 25,882*D1,725 with R2: 0,8561).

The clean reaction of 5-lithio-6-diisopropylphosphinoacenaphthene (1') with dichlorophosphines, RPCl₂ (R = Ph, Fc, NMe₂, iPr), led to the formation of peri-substituted phosphino-phosphonium chloride salts 2-5. The synthetic utility of these salts was demonstrated in a range of reactions. Mixed tertiary/secondary bis(phosphines) (6 and 7) were prepared by the LiAlH₄ reduction of phenyl or ferrocenyl phosphino-phosphoniums (2 and 3), and the bis(borane) adduct of 6 was prepared by reduction of 2 with BH₃•SMe₂. Reaction of 2 and 3 with a large excess of MeOTf at elevated temperature gave 1,2-diphosphoniums (11 and 12), which were subjected to reduction and co-ordination to a molybdenum(0) centre. An investigation into the co-ordination chemistry of 2 revealed three distinct modes of reactivity. In the reaction with [(nor)Mo(CO)₄] the Mo(0) complex [(2)Mo(CO)₄Cl] (18) was isolated, in which monodentate co-ordination was observed. [PtCl₂(cod)] reacts with the chloride and triflate salts of 2 to form [(2Cl)PtCl₂] (19) and [((2Cl)PtCl)₂][TfO]₂ (21) respectively, both of which show co-ordination of 2 as a bidentate phosphine/chlorophosphine ligand. A palladium(II) dimer (22) in which 2 forms a chelating phosphine/phosphide ligand was isolated from the oxidative addition of 2 to a palladium(0) complex. The geminally bis(peri-substituted) tridentate phosphine (27) was prepared by reaction of 1' with half an equivalent of iPrPCl₂. 27 has a rather strained geometry, and displays restricted dynamics on an NMR timescale, which leads to anisochronicity of all three phosphorus nuclei at low temperatures. Strained bis and tris(sulfides) 28 and 29 and the bis(selenide) 30 have been isolated from the reaction of 27 with sulfur and selenium, respectively. A series of co-ordination complexes, [(27)Cu(MeCN)][BF₄] (32), [(27)PtCl][Cl] (33), [(27)FeCl₂] (34) and fac-[(27)Mo(CO)₃] (35), with tetrahedral, square planar, trigonal bipyramidal and octahedral geometries, respectively, were synthesised. In all of these complexes the tris(phosphine) backbone is distorted, but to a significantly smaller extent that in the chalcogenides 28-30.

The formation of the Gulf Co-operation Council (GCC) in 1981 was perceived by most observers to be a collective security response to the Iran-Iraq war. Despite this view, the group has endured ten years of integration in a turbulent region and has survived: external threats to its sovereignty, Islamic fundamentalism, the decline of oil prices, internal unrest, attempted coups, and the invasion and occupation of a constituent member. This poses the question: has the integration of these countries proved to be a success? This thesis attempts to answer this question with the aid of a three dimensional analysis. The first dimension examines the theory and practice of integration. Its primary objective is to provide an insight into integration. As the GCC can, at best, be categorised as a Customs Union, this chapter concentrates on Free Trade Areas and Customs Union theories and explores their relationships with tariffs, protectionism, developing countries, and politics. A review of the empirical analyses in the field is essential due to the fact that a mathematical technique is applied to GCC trade in the latter part of this thesis. The existence of political, economic and manpower factors are found to be more detrimental to the GCC's interests than its adherence or convergence to the theory and practice of integration. An analysis of these three factors constitutes the second dimension of the thesis. This commences by examining the Islamic antecedents of the member countries, pan-Islamism and nationalism in the 19th century, and Middle Eastern efforts at integration from the decline of the Ottoman Empire to the present. The establishment of the existing GCC nations and an examination of their natural resources, demography, industry, infrastructure, agriculture, and fisheries is covered, as is the impact of the 1990-91 occupation of Kuwait and the BCCI liquidation. A review of manpower factors includes an examination of the labour market in the pre and post 1973 period with emphasis given to the role of expatriate and indigenous labour. In addition, the influence of education, women in the workforce, nationality, and residence policies on indigenous labour is discussed. The third dimension reviews the prospects of the GCC. This is performed through the construction and utilisation of matrices which examine the similarity or dissimilarity of GCC trade to the World, Developed and Developing Countries. United Nations Standard Industrial Trade Category (SITC) data up to 3-digits, has been used to construct twenty seven 22 x 22 matrices. Nine of these matrices indicate GCC trade with the Rest of the World and are linked to economic and financial literature on the Gulf in order to examine their credibility. Eighteen matrices which indicate trade with the Developing and Developed World indentify potential trade creation, trade diversion and prospects. It is the conclusion of the thesis that the GCC has not succeeded in its integration efforts. The lack of co-ordination to perform as a single unit in economic, political, and military areas, the undemocratic political systems, the exploitation of expatriate labour, the segregation of indigenous labour, and most importantly, the wasted opportunities indicated by the matrices of greater trade creation with the Developed and Developing Countries contribute significantly to the ineffectiveness of the group.

Prepaid dental care - a questionnaire on dentalstaff attitudes and contract management   Abstract Background: In order to get young people to maintain a continued regular contact with dental care, after they are regarded as paying adults, prepaid dental care was introduced in Västra Götaland in 2007. Prepaid dental care is a payment model in which patients pay a specific amount for their dental care over a three-year period, monthly or annually. Since prepaid dental care is a major part of the daily work in public dental care, it is important to examine the dental staff's attitudes to this payment model.  Purpose: The purpose of this study was to investigate the dental staff's handling of prepaid dental care and their attitudes regarding this payment model in the Public Dental Service in Region Kalmar County. Method: A questionnaire study based on a quantitative approach with certain issues analysed by qualitative method was performed. Surveys were sent to all employees at all 18 general dental clinics belonging to Region Kalmar County Public dental service. In total 133 employees answered the questionnaire.  Result: Respondents generally had a positive view on prepaid dental care. Regarded as positive was for example the opportunity of regular individualized treatment independent of costs. The main drawback, according to the respondents, was that patients who do not have prepaid dental care are not given any priority for being summoned for examination. Most respondents offer contracts to the majority of the patients and regardless of the price class. Conclusion: Prepaid dental care was considered positive, favouring both the clinic and the patients who chose this payment model. Although it should be taken into consideration that patients without prepaid dental care are not prioritised to be summoned for treatment compared to patients with prepaid dental care. The majority of the respondents are in agreement that prepaid dental care can impair the care situation of patients without contract.     Keywords: Dental Insurance payment, Dental staff, Prepaid dental care, R2, Region Kalmar Län / Bakgrund:För att få ungdomar att behålla en fortsatt regelbunden kontakt med tandvården, efter det att de betraktas som betalande vuxna, startades 2007 Frisktandvård i Västra Götaland. Frisktandvård innebär en betalmodell där patienter under en 3 årsperiod, månadsvis eller årsvis betalar en specifik summa för sin tandvård. Eftersom Frisktandvård utgör en stor del av det dagliga arbetet inom folktandvården är det viktigt att undersöka tandvårdspersonalens hantering och attityd till Frisktandvård. Syfte:Syftet med denna studie var att inom Folktandvården i Region Kalmar Län undersöka tandvårdspersonalens hantering av Frisktandvård och deras attityder gällande denna betalmodell. Metod: Enenkätstudie med både slutna och öppna frågor som analyserades genom både kvantitativ och kvalitativ metodik. Enkäter skickades ut till samtliga medarbetarna på 18 allmänna tandvårdskliniker i Region Kalmar Län. Totalt besvarade 133 medarbetare enkäten. Resultat: Respondenterna hade överlag en positiv syn på Frisktandvård. Som positivt ansågs möjlighet för regelbunden individanpassad behandling oberoende av kostnader. Den främsta nackdelen med Frisktandvård enligt respondenterna var att patienter som inte har avtal ej heller prioriteras vid kallelser. Merparten respondenter erbjuder Frisktandvård till de flesta patienter samt i alla prisklasser. Slutsats: Frisktandvård ansågs som en positiv möjlighet enligt respondenterna som i sin helhet gynnar både kliniken och de patienter som har avtal. Det bör dock beaktas att kallelser för patienter utan avtal inte prioriteras i jämförelse med patienter med avtal Majoriteten av respondenterna anser att Frisktandvård kan försämra vårdsituationen för patienter utan avtal.     Nyckelord: Frisktandvård, R2, Region Kalmar Län, Tandvårdspersonal, Tandvårdsstöd

The present research work focuses on the coordination chemistry of two different types of monoanionic nitrogen-coordinating ligands, namely the bidentate triazenide ligand [(DippN)N(NDipp)]⁻ (Dipp = Prⁱ₂C₆H₃−2,6) (L¹) and monodentate arylamido ligands [N(R)(Ar)]⁻ (R = SiMe₃., Ar = C₆H₃Me₂-2,6 (L²), C₆H₂Me₃-2,4,6 (L³) or C₆H₃Prⁱ₂-2,6 (L⁴); R = SiBuᵗMe₂, Ar = C₆H₃Prⁱ₂-2,6 (L⁵)). The first part of this work was centred on the synthesis, structural characterization and reactivity of divalent lanthanide metal complexes derived from the triazenide ligand L¹. The second part of this work dealt with the chemistry of low valent and low-coordinate first row transition metal complexes supported by arylamido ligands Lⁿ (n = 2-5). The last part of this work focused on the synthesis and structures of divalent chromium complexes derived from the L¹, L⁴ and L⁵ ligands. / Chapter 1 presents an overview on divalent lanthanide complexes derived from nitrogen-coordinating ligands. The coordination chemistry of low valent and low-coordinate first-row transition metal complexes was also reviewed. / Chapter 2 describes the preparation and characterization of samarium(II) triazenide complex [Sm(L¹)₂(THF)₂] (2). Complex 2 was prepared by the reaction of SmI₂(THF)₂ with 2 equivalents of potassium triazenide [KL¹(THF)₀.₅] (1). The electrochemistry of 2 in THF was studied with cyclic voltammetry. Complex 2 is a strong reducing reagent. Its reactions with various inorganic/organic substrates have been examined. Treatment of 2 with AgCl or PhCH₂Cl gave Sm(III) bis(triazenide) chloride complex [Sm(L¹)₂Cl(THF)₂] (3), whilst reaction of 2 with I₂ led to the isolation of the iodide complex [Sm(L¹)I₂(THF)₃] (4). Reactions of 2 with PhEEPh (E = S, Se) afforded the corresponding Sm(III) chalcogenolate complexes [Sm(L¹)₂(EPh)(THF)] (E = S (5), Se (6)). On the other hands, addition of 2 to ArEEAr (Ar = Buᵗ₂C₆H₃−2,6, E = S, Se and Te) yielded the homoleptic Sm(III) tris(triazenide) complex [Sm(L¹)₃] (7) as the only isolable product. Besides, reactions of 2 with O₂, S₈, Se, Ph₃P=Se and BuᵗOOBuᵗ also yielded complex 7. Complex 2 reacted with PhNHNH₂ and PhNHNHPh, leading to the isolation of the corresponding Sm(III) phenylhydrazido complexes [Sm(L¹)₂(DMAP)₂(NH₂NPh)] (8) and [Sm(L¹)(THF)(μ-η²:η²-PhNNPh)]₂ (9). Reactions of 2 with azobenzene, benzophenone, 9-fluorenone, adamantyl azide, N, N’-dicyclohexylcarbodiimide, N, N’-diisopropylcarbodiimide, and CS₂ were examined as well. / Chapter 3 reports on the coordination chemistry of the triazenide ligand L¹ with divalent ytterbium and europium ions. Metathetical reaction of LnI₂(THF)₂ (Ln = Yb, Eu) with two molar equivalents of [Na(L¹)(THF)₃] (10) led to the corresponding divalent lanthanide(II) bis(triazenide) complexes [Eu(L¹)₂(THF)₂] (11) and [Yb(L¹)₂(THF)₂] (12). The heteroleptic ytterbium(II) complex [Yb(L¹)(μ-I)(THF)₂]₂.(C₆H₁₄) (13.C₆H₁₄) was also isolated along with 12. Oxidation of 12 with CuCl afforded Yb(III) triazenide−chloride complex [Yb(L¹)₂Cl(THF)₂] (14). Treatment of 12 with PhEEPh (E = S, Se) afforded the corresponding Yb(III) chalcogenolate complexes [Yb(L¹)₂(EPh)(THF)] (E = S (15), Se (16)). Nevertheless, reactions of 12 with elemental sulfur and selenium yielded the homoleptic Yb(III) complex [Yb(L¹)₃] (17) as the only isolable product. / Chapter 4 deals with the synthesis and characterization of low valent and low-coordinate first row transition metal complexes derived from arylamido ligands L²-L⁵. Reaction of MCl₂ (M = Fe, Co) with one molar equivalent of lithium amide [Li(L³)(TMEDA)] (TMEDA = Me₂NCH₂CH₂NMe₂) yielded the corresponding monoamido complexes [M(L³)Cl(TMEDA)] (M = Fe (20) and Co (22)). Reduction of [Co(L²)Cl(TMEDA)] (21), 22 and [Co(L³)Cl(TMEDA)] (23) with potassium metal gave the corresponding cobalt(I) amido complexes [CoL²]₂ (24), [CoL₃]₂ (25) and [CoL⁴]₂ (26), respectively. Meanwhile, treatment of [Fe(L⁴)Cl(TMEDA)] (23) with potassium metal yielded iron(I)-dinitrogen complex [{FeL⁴(TMEDA)}₂(μ-η¹:η¹-N₂)] (27). Complexes 24-27 were fully characterized by X-ray crystallography, various spectroscopic techniques and cyclic voltammetry. DFT calculations were carried out in order to understand the electronic structures of these complexes. / Chapter 5 describes the preparation and characterization of three neutral two-coordinate first row transition metal complexes of the general formula [M(L⁵)₂] (M = Fe (29), Co (30), Ni (31)). They were prepared by the reactions of anhydrous MCl₂ (M = Fe, Co) or NiBr₂(DME) with [LiL⁵(Et₂O)₂] (28). The solid-state structures of complexes 29-31 were determined by X-ray diffraction analysis. They were also characterized by spectroscopic methods (UV/Vis, I.R.) and electrochemistry. TD-DFT computational analysis was carried out in order to assign UV/Vis spectra features of these two-coordinate late transition metal (Fe->Ni) complexes. / Chapter 6 reports on the coordination chemistry of L¹, L⁴ and L⁵ with chromium ions. Treatment of CrCl₂ or CrCl₃ with one molar equivalent of [Li(L¹)(Et₂O)₂] (32) yielded heteroleptic Cr(II) complex [Cr(L¹)(μ-Cl)(THF)]₂ (33) and Cr(III) complex [Cr(L¹)Cl₂(THF)₂] (34), respectively. Attempts to reduce 33 and 34 with potassium metal, potassium graphite or magnesium were unsuccessful, yielding [Cr(L¹)₂] (35). Reaction chemistry of 35 was also studied in our research work. No reaction was observed in the reaction of 35 with PhEEPh (E = S, Se). Treatment of 35 with iodine led to the isolation of iodide bridged heteroleptic Cr(II) complex [Cr(L¹)(μ-I)(THF)]₂ (36). Simple monodentate amido ligands L⁴ and L⁵ were also used to prepare Cr(I) complexes. Treatment of anhydrous CrCl₂ with [LiL⁴(Et₂O)₀.₅] and [LiL⁵(Et₂O)₂] (28) afforded oxidative deprotonation products [Cr{N(C₆H₃Prⁱ₂-2,6)(SiMe₂CH₂)}₂Cr(L⁴)] (37) and [Cr(L⁵){N(C₆H₃Prⁱ₂-2,6)(SiBuᵗMeCH₂)}] (38). Attempts to synthesize monovalent chromium complexes supported by the L¹, L⁴ and L⁵ ligands were still in progress during the submission of this thesis. / Chapter 7 summarizes the results of the present studies. A brief description on the future direction of this research work is also presented. / 本項研究工作主要針對兩類負一价含氮配体，即雙齒叠氮基配体[(DippN)N(NDipp)]⁻ (Dipp = Prⁱ₂C₆H₃−2,6) (L¹)和單齒苯胺基配体[N(R)(Ar)]⁻ (R = SiMe₃, Ar = C₆H₃Me₂-2,6 (L²), C₆H₂Me₃-2,4,6 (L³) or C₆H₃Prⁱ₂-2,6 (L⁴); R = SiBuᵗMe₂, Ar = C₆H₃Prⁱ₂-2,6 (L⁵))的配位化學進行研究。本研究工作的第一部分致力於研究二價鑭系叠氮基配合物的合成，結構及其化學反應性。第二部分研究工作主要集中于由苯胺基構築的低價態，低配位數的第一周期后過渡金属的配位化學研究。最後一部分工作闡述了二價鉻叠氮基配合物和苯胺基配合物的合成，結構和表徵。 / 第一章概述了二價鑭系含氮配合物的發展。同時，也簡要闡述低價態，低配位數過鍍金属含氮配合物的研究工作。 / 第二章描述了二價釤叠氮基配合物[Sm(L¹)₂(THF)₂] (2)的製備，結構及其化學反應性。配合物2是由SmI₂(THF)₂與兩當量的鉀叠氮基化合物[KL¹(THF)₀.₅] (1) 反應製得。配合物2的電化學性質採用了循環伏安法進行了研究。介於配合物2為強還原劑，它與一系列無機/有機化合物的反應也予以探索。配合物2與AgCl或PhCH₂Cl反應得到了三價釤雙叠氮基氯化物[Sm(L¹)₂Cl(THF)₂](3)，同時配合物2與單質碘I₂反應得到了碘化物[Sm(L¹)I₂(THF)₃] (4)。配合物2與二苯基硫族化合物PhSSPh及PhSeSePh反應得到了相應的三價釤硫族配合物[Sm(L¹)₂(EPh)(THF)](E = S (5), Se (6))。與之相反，配合物2與位阻較大的二苯基硫族化合物ArEEAr (Ar = Buᵗ₂C₆H₃−2,6, E = S, Se和Te)反應得到了均配的三價釤三叠氮基配合物[Sm(L¹)₃] (7)。此外，配合物2與O₂, S₈, Se, Ph₃P=Se和BuᵗOOBuᵗ反應都生成了配合物7。配合物2與苯肼化合物PhNHNH₂和PhNHNHPh反應得到了相應的三價釤苯肼配合物[Sm(L¹)₂(DMAP)₂(NH₂NPh)] (8) (DMAP = 對二甲基胺吡啶)以及[Sm(L¹)(THF)(μ-η²:η²-PhNNPh)]₂(9)。另外，本章對配合物2與偶氮苯;二苯基酮;9-芴酮;金剛烷叠氮化物;二環已基碳二亞胺;二異丙基碳二亞胺以及二硫化碳的反應性也進行了研究。 / 第三章講述了對該叠氮基配体L¹所衍生出的二價鐿和銪配合物的配位化學研究工作。二價鑭系碘化物LnI₂(THF)₂(Ln = Yb, Eu)與兩當量的鈉叠氮基化合物[Na(L¹)(THF)₃] (10)的複分解反應得到相應的二價鑭系雙叠氮基配合物[Eu(L¹)₂(THF)₂] (11)以及[Yb(L¹)₂(THF)₂] (12)。在製備二價鐿雙叠氮基配合物[Yb(L¹)₂(THF)₂] (12)的過程中同時得到了異配的二價鐿碘橋連單叠氮基配合物[Yb(L¹)(μ-I)(THF)₂]₂.(C₆H₁₄) (13.C₆H₁₄)。配合物12與CuCl的氧化反應得到三價鐿叠氮基氯化物[Yb(L¹)₂Cl(THF)₂] (14)。此外，配合物12與二苯基硫族化合物PhSSPh及PhSeSePh反應得到了相應的三價鐿硫族配合物[Yb(L¹)₂(EPh)(THF)] (E = S (15), Se (16))。然而，配合物12與單質硫和單質硒的反應生成唯一的產物，即均配的三價鐿三叠氮基配合物[Yb(L¹)₃] (17)。 / 第四章闡述了由苯胺基配体L²-L⁵所衍生的低價態，低配位數第一周期后過渡金屬的製備以及結構表徵。通過金屬氯化物MCl₂(M = Fe, Co)和一當量的鋰苯胺基化合物反應得到相應的二價鐡和鈷的單苯胺基配合物[M(L³)Cl(TMEDA)] (M = Fe (20) 和 Co (22))。配合物[Co(L²)Cl(TMEDA)] (21), 22和[Co(L³)Cl(TMEDA)] (23) 與金屬鉀的還原反應分別得到相應的一價鈷苯胺基配合物[CoL²]₂ (24), [CoL³]₂ (25) 和 [CoL⁴]₂ (26)。與此同時，二價鐡單苯胺基配合物[Fe(L⁴)Cl(TMEDA)] (23)與金屬鉀反應得到了一價鐡-偶氮配合物[{FeL⁴(TMEDA)}₂(μ-η¹:η¹-N₂)] (27)。配合物24-27的分子結構及其物理性質分別以X射綫衍射晶体學，波譜學以及循環伏安法表徵。密度泛函(DFT)這一理論計算方法也被用來瞭解這些配合物的電子結構。 / 第五章描述了三個二配位的第一周期后過渡金屬配合物[M(L⁵)₂] (M = Fe (29), Co (30), Ni (31))的製備和表徵。它們由相應的無水金屬鹵化物MCl₂ (M = Fe, Co)或NiBr₂(DME)與[LiL⁵(Et₂O)₂] (28)反應製得。配合物29-31的固體結構由X射綫衍射分析獲得。它們的光學性質和電學性質也分別由波譜方法（紫外可見光光譜，紅外光譜）以及循環伏安法表徵得到。含時密度泛函(TD-DFT)這一計算分析方法也被用來瞭解這些化合物紫外可見光光譜性質。此外，配合物31在有機烯烴與苯硅烷PhSiH3的硅氫化反應中被證實為有效的催化劑。 / 第六章講述了由配体L¹, L⁴與L⁵所構築的二價鉻的配位化學的研究。通過無水二氯化鉻CrCl₂或三氯化鉻CrCl₃與一當量的鋰叠氮基配合物[Li(L¹)(Et₂O)₂] (32)反應分別成功製備了相應的異配的二價鉻配合物[Cr(L¹)(μ-Cl)(THF)]₂ (33) 以及三价鉻配合物[Cr(L¹)Cl₂(THF)₂] (34)。利用金屬鉀，鉀碳以及單質鎂來還原配合物33和34生成了二價鉻雙叠氮基配合物[Cr(L¹)₂] (35)。此外，配合物35的反應性能也在本項工作得以研究。然而，在配合物35與二苯基硫族化合物PhSSPh及PhSeSePh反應中並沒有觀察到明顯的反應變化，依舊得到了原料配合物35。配合物35與單質碘I₂反應得到了異配碘橋連二價鉻配合物[Cr(L¹)(μ-I)(THF)]₂ (36)。單齒苯胺基配体L⁴和L⁵也被嘗試用來合成一價鉻配合物。無水二氯化鉻CrCl2與鋰苯胺基化合物[LiL⁴(Et₂O)₀.₅]和[LiL⁵(Et₂O)₂] (28)反應分別生成了氧化脫質子產物[Cr{N(C₆H₃Prⁱ₂-2,6)(SiMe₂CH₂)}₂Cr(L⁴)] (37) and [Cr(L⁵){N(C₆H₃Prⁱ₂-2,6)(SiBuᵗMeCH₂)}] (38)。關於利用叠氮基配体L¹，以及苯胺基配体L⁴和L⁵來製備一價鉻配合物的相關工作在遞交本論文的過程中还在進行中。 / 第七章總結了本論文的研究成果，並對本項工作未來的發展作出了簡要的描述。 / Yun, Lei. / Thesis (Ph.D.)--Chinese University of Hong Kong, 2015. / Includes bibliographical references. / Abstracts also in Chinese.80-30|aDetailed summary in vernacular field only. / Title from PDF title page (viewed on 21, December, 2016). / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only. / Detailed summary in vernacular field only.