La mise en œuvre de la Résonance Magnétique Nucléaire pour l’étude des complexes hôtes-invitées est assez répandue. Cependant, les complexes entre un calixarène (comme le p-sulfonatocalix[4]arène que nous avons utilisé ici) et des cations métalliques monovalents (comme le césium et le thallium qui font l’objet de cette thèse) n’ont été jusqu’ici étudiés qu’au moyen de mesures de déplacement chimique. Hormis les mesures de déplacement chimique, cette thèse s’appuiera essentiellement sur les paramètres dynamiques déterminés par RMN. La première idée était de mesurer les coefficients d’auto-diffusion de la molécule d’hôte et de l’invité. Cette technique RMN, permettant de telles mesures, semblait suffisamment développée pour apporter des informations sur la nature du complexe (inclusion dans la cavité de calixarène), sa stœchiométrie ou encore la constante d’association. Nous avons également pu profiter de la richesse d’informations provenant de la relaxation de spin. Ces informations sont à la fois de nature structurale et dynamique et ont permis de caractériser ces complexes de façon très précise. La relaxation des carbones-13 du calixarène lui-même a été efficacement complétée par la relaxation longitudinale et la relaxation transversale des deux cations. Non seulement l’inclusion dans la cavité a été confirmée pour les deux cations, mais la localisation précise de ces cations a pu être déterminée grâce au mécanisme d’anisotropie de déplacement chimique qui, également, met bien en évidence les interactions cation- . Nous avons donc montré la parfaite cohérence de l’interprétation des divers paramètres RMN pour la caractérisation des deux complexes. / Nuclear Magnetic Resonance spectroscopy is widely used for the study of host-guests complexes. However, the complexes between a calixarene (as the p-sulfonatocalix[4]arene which we used here) and monovalent metal cations (as cesium and thallium which are the subject of this thesis) were until know studied only by chemical shift measurements. In addition to chemical shift, this thesis will be primarily based on the dynamic parameters determined by NMR. The first idea was to measure the self-diffusion coefficients of the host and guest molecules. The relevant NMR technique which allows such measurements seems sufficiently developed so as to provide information on the nature of the complex (inclusion in the cavity of calixarene), its stoichiometry or its association constant. We then exploited the wealth of information arising from spin relaxation measurements. This information, known to be of both structural and dynamic nature, made it possible the characterization of these complexes in a very precise way. The carbons-13 relaxation measurements of calixarene itself were actually supplemented by the longitudinal and the transverse relaxation measurements of the two cations. Not only the inclusion of the two cations in the cavity was confirmed, but the precise localization could be obtained through the chemical shift anisotropy mechanism, which also, demonstrates clearly the existence of cation- interactions. We thus showed the perfect consistence of the interpretation of various NMR parameters for the characterization of the complexes studied in this thesis.

No description available.

This thesis is principally concerned with the interaction of cobalt porphyrin complexes with halocarbons. There have been no previous studies of these, despite the afct that the ability to readily introduce substituents into the porphyrin ligand makes it ideal for inducing subtle electronic and steric changes into the complexes. The reactions of various substituted cobalt tetraphenylporphyrins with halocazbons was studied. Three series of experiments were performed involving activation by heat, visible light and ultraviolet light. Products were characterized by electronic, nmr and mass spectrometry. The five coordinate complexes, [CoX (Por)] , obtained from thermally activated reactions and those performed with uv irradiation under nitrogen, proved particularly difficult to characterize since they are subject to disproportionation giving paramagnetic products. This aspect is discussed in detail and the results obtained allow clarification of conflicting reports in the literature. A qualitative investigation of relative reaction rates has led to the tentative suggestion that thermal reactions proceed by an electron transfer mechanism, whereas an atom abstraction mechanism applies to reactions involving activation by ultraviolet light. No reaction took place between cobalt porphyrins and the substrates in the presence of visible light. Aerobic ultraviolet radiation results in the formation of cobalt porphyrin [pi]-cation radicals with either a1u or azU. ground states, depending on the substituent pattern of the porphyrin. The cobalt porphyrins were all shown to possess catalytic activity for halocarbon-alkene addition reactions. Furthermore, studies in this area suggest that the catalytic activity could be correlated wíth the substituent pattern on the porphyrin ligand and, thus, complements the studies described above. A related rhodium complex was also synthesized and examined but was shown to have a disappointingly low catalytic activity. Products of [RuC1[sub]2z(PPh[sub]3)[sub]3] -catalysed additions of halocarbons to cyclohexa-1,3-diene were investigated by chromatographic and spectroscopic analyses to ascertain the stereochemistry of the products. The ratio of the two isomeric products was found to depend on steric effects of the addend groups, CX[sub]3 (X = Cl, Br) and X (X = Cl, Br).

by Tung Suet Lam. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgments --- p.iv / Abstract --- p.v / Abstract (Chinese version) --- p.vii / Abbreviations --- p.ix / List of Compounds --- p.xi / Chapter Chapter1. --- synthesis and structures of iron(ii) and cobalt(ii) complexes derived from pyridine-functionalized amido ligands / Chapter 1.1 --- INTRODUCTION --- p.1 / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- A Brief Review on Amides of the Late Transition Metals --- p.3 / Chapter 1.2 --- OBJECTIVES OF THIS WORK --- p.5 / Chapter 1.3 --- RESULTS AND DISCUSSION --- p.7 / Chapter 1.3.1 --- Alkali Metal Derivatives of N-Silylated 2-Aminopyridines --- p.7 / Chapter 1.3.1.a. --- "Synthesis of Aminopyridines [HN(SiMe3)》(2-C5H3N-6-R)] (R=H (1a), Me (1b)) and Their Lithium Derivatives" --- p.7 / Chapter 1.3.1.b. --- Synthesis of the Potassium Derivative [{K(L1)(tmeda)}2 ] (4) --- p.8 / Chapter 1.3.1.c. --- "Physical Characterization of Compounds 2a, 3 and" --- p.4 9 / Chapter 1.3.1.d. --- Molecular Structures of Compounds 3 and4 --- p.10 / Chapter 1.3.2 --- "Synthesis, Structures and Reactivities of Iron(II) and Cobalt(II) Amides" --- p.16 / Chapter 1.3.2.a. --- Synthesis of Mononuclear Iron(II) and Cobalt(II) Diamides --- p.16 / Chapter 1.3.2.b. --- Physical Characterization of Compounds 5-8 --- p.16 / Chapter 1.3.2.C. --- Molecular Structures of Compounds 5-8 --- p.17 / Chapter 1.4 --- EXPERIMENTAL FOR CHAPTER1 --- p.28 / Chapter 1.5 --- REFERENCES FOR CHAPTER1 --- p.31 / Chapter Chapter2. --- reaction of iron(II) and cobalt(II) amides with phenolic compounds / Chapter 2.1 --- "SYTHESIS, STRUCTURES AND REACTIVITIES OF IRON(II) AND COBALT(II) BIS(ARYLOXIDE)" --- p.36 / Chapter 2.1.a. --- "Reaction of Compounds 7 and 8 with 2,2 -ethylidenebis(4,6-di-tert-butyl phenol)" --- p.36 / Chapter 2.1.b. --- "Molecular Structures, Magnetic Moments, and Reactivities of Compounds 9and10" --- p.36 / Chapter 2.2 --- A GENERAL REVIEW ON CATECHOL DIOXYGENASES --- p.44 / Chapter 2.3 --- "SYTHESIS, STRUCTURES AND REACTIVITIES OF IRON(II) AND COBALT(II) CATECHOLATES" --- p.46 / Chapter 2.3.a. --- Synthesis of Binuclear Iron(II) and Cobalt(II) Catecholates --- p.46 / Chapter 2.3.b. --- Molecular Structures of Compounds 11 and12 --- p.48 / Chapter 2.3.c. --- Reactions of Compounds 11 and 12 with Dioxygen --- p.54 / Chapter 2.3.d. --- Identification of Oxidative Cleavage Products --- p.54 / Chapter 2.4 --- EXPERIMENTAL FOR CHAPTER2 --- p.56 / Chapter 2.5 --- REFERENCES FOR CHAPTER2 --- p.59 / Chapter Chapter3. --- synthesis of late transition metal amidinates / Chapter 3.1 --- INTRODUCTION --- p.62 / Chapter 3.1.1 --- General background --- p.62 / Chapter 3.1.1.a --- Metal´ؤAmidine Bonding Modes --- p.63 / Chapter 3.1.1.b. --- Preparation of Metal Amidinates Complexes --- p.64 / Chapter 3.1.2 --- "N-Silylated Benzamidinates of Li, Na and K 一 The Starting Materials" --- p.65 / Chapter 3.1.3 --- A General Review on The Chemistry of Low-Valent Late Transition- Metal Amidinates --- p.67 / Chapter 3.2 --- OBJECTIVES OF THIS WORK --- p.72 / Chapter 3.3 --- RESULTS AND DISCUSSION --- p.73 / Chapter 3.3.1 --- Synthesis and Structures of Lithium Benzamidinates --- p.73 / Chapter 3.3.1.a. --- "Synthesis of [Li(L3)(tmeda)] (L3 = [PhC(NSiMe3){N(2,6´ؤ Me2C6H3}]) and [Li(L4)(tmeda)] (L4 = [PyC(NSiMe3){N(2,6- Me2C6H3)}]) as Ligand´ؤTransfer Reagents" --- p.73 / Chapter 3.3.1.b. --- Physical Characterization of Compounds 15 and16 --- p.74 / Chapter 3.3.1.c. --- Molecular Structures of Compounds 15 and16 --- p.75 / Chapter 3.3.2 --- "Synthesis, Structures and Reactivities of Iron(II) and Cobalt(II) Amidinates" --- p.81 / Chapter 3.3.2.a. --- Synthesis of Mononuclear Iron(II) Benzamidinates --- p.81 / Chapter 3.3.2.b. --- Synthesis of a Binuclear Cobalt(II) Benzamidinate --- p.82 / Chapter 3.3.2.c. --- Physical Characterization of Compounds 17-19 --- p.83 / Chapter 3.3.2.d. --- Molecular Structures of Compounds 17-19 --- p.84 / Chapter 3.3.2.e. --- Reaction of Compound 18 with Dioxygen --- p.94 / Chapter 3.3.2.f. --- Molecular Structure of Compound20 --- p.95 / Chapter 3.3.3 --- Synthesis and Structures of Nickel(II) and Copper(I) Benzamidinates --- p.98 / Chapter 3.3.3.a --- Synthesis of a Nickel(II) Benzamidinate --- p.98 / Chapter 3.3.3.b. --- Synthesis of a Binuclear Copper(I) Benzamidinate --- p.99 / Chapter 3.3.3.c. --- Physical Characterization of Compounds 21 and22 --- p.101 / Chapter 3.3.3.d. --- Molecular Structures of Compounds 21 and22 --- p.102 / Chapter 3.3.4 --- Synthesis and Structures of Mononuclear Zinc(II) and Cadmium(II) Amidinates --- p.107 / Chapter 3.3.4.a --- Synthesis of Mononuclear Zinc(II) and Cadmium(II) Benzamidinates --- p.107 / Chapter 3.3.4.b. --- Physical Characterization of Compounds 23 and24 --- p.107 / Chapter 3.3.4.C. --- Molecular Structures of Compounds 23 and24 --- p.108 / Chapter 3.4 --- EXPERIMENTAL FOR CHAPTER3 --- p.113 / Chapter 3.5 --- REFERENCES FOR CHAPTER3 --- p.119 / appendix1 --- p.127 / appendix2 --- p.129

The rocks of the Challis Volcanic Group, Idaho are investigated and constraints on their petrogenesis used to evaluate the tectonic control on the formation of early, extensionassociated magmatism in the western U. S. A. New and published 40Ar-39Ar analyses indicate that the rocks of the Challis Volcanic Group erupted between - 50 and 45 Ma at extrusion rates estimated at 0.01 to 0.03 km3 yr 1. The rocks have high-K calcalkaline/ shoshonitic compositions and incompatible trace element analyses show them to be LILE and LREE enriched ((La/Yb) -7 to 20) but relatively depleted in Nb, Ta and Ti (e. g. Nb/La < 0.5 in the main). All rocks have high initial 87Sr/86Sr (0.70673 to 0.71135) and low 143Nd/144Nd (0.51151 to 0.51234) ratios in comparison to oceanic basalts. The rocks are interpreted to result from partial melting in both spinel and garnet facies of heterogeneousm, ajor elementd epleted,L REE enriched but Nb, Ta and Ti depletedp eridotite source regions in the lithospheric mantle. The origin of these LREE enriched source regions is most probably related to mantle metasomatism in a subduction zone tectonic setting, although the' age of these events are not constrained. The petrogenesis of the Challis Volcanic Group is broadly similar to early magmatism from areas of the Cordillera to the south (e. g. Colorado River Trough), but contrasts with areas to the north where crustal melting apparently dominates (e. g. northern Idaho: Omineca Belt). Thus it is suggested that the syn-compression thermal history of the Cordillera, immediately prior to extension and early magmatism, varies significantly between southern and northern Idaho. This variation correlates spatially with the northern limit of compression within the Laramide Foreland Province (. 75 to 45/30 Ma). Compressional deformation within the Laramide Foreland Province may be coincident with a period of sub-horizontal subduction and therefore partial melting of the mantle lithosphere may be related to the removal of this subducted slab from beneath the lithosphere, although this remains poorly constrained. A comparison is made between the Challis Volcanic Group and Archaean sanukitoids, to suggest that the Tertiary rocks may provide a tectonomagmatic analogue for these particular late Archaean rocks. The implications of this comparison for late Archaean tectonics and crustal growth are discussed.

Lam, Pui Chi. / Thesis submitted in: November 2006. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references. / Abstracts in English and Chinese. / Table of Contents --- p.i / Acknowledgements --- p.v / Abstract --- p.vi / 摘要 --- p.viii / List of Compounds --- p.x / Abbreviations --- p.xiii / Chapter CHAPTER 1. --- A GENERAL INTRODUCTION TO METAL AMIDES / Chapter 1.1 --- GENERAL BACKGROUND --- p.1 / Chapter 1.2 --- OBJECTIVES OF THIS WORK --- p.7 / Chapter 1.3 --- REFERENCES FOR CHAPTER1 --- p.8 / Chapter CHAPTER 2. --- SYNTHESIS AND STRUCTURES OF GROUP 4 METAL AMIDES / Chapter 2.1 --- INTRODUCTION --- p.15 / Chapter 2.1.1 --- General Background --- p.15 / Chapter 2.1.2 --- Common Preparation Methods for Group 4 Metal Amides --- p.15 / Chapter 2.1.3 --- "An Overview on Titanium(IV), Zirconium(IV) and Hafnium(IV) Amides" --- p.17 / Chapter 2.2 --- AIMS OF OUR STUDIES --- p.26 / Chapter 2.3 --- RESULTS AND DISCUSSION --- p.27 / Chapter 2.3.1 --- Synthesis of the Ligand Precursor (HL1) and the Corresponding Lithium Derivative [Li(L1tmeda)] --- p.27 / Chapter 2.3.2 --- Synthesis and Structures of Monomeric and Dimeric Titanium(IV) Amides --- p.28 / Chapter 2.3.2.1 --- Synthesis of [Ti(L1 )Cl2(μ-Cl)2] (V and [TiL1)Ch3(THF)] (4) --- p.28 / Chapter 2.3.2.2 --- Reactivity Studies --- p.31 / Chapter 2.3.2.3 --- Physical Characterization of Compounds 3 and 4 --- p.33 / Chapter 2.3.2.4 --- Molecular Structures of Compounds 3 and 4 --- p.36 / Chapter 2.3.3 --- Synthesis and Structures of Mononuclear Zirconium(IV) and Hafnium(IV) Amides --- p.44 / Chapter 2.3.3.1 --- Synthesis of[M(L1)3Cl] (M = Zr 5 and Hf6) --- p.44 / Chapter 2.3.3.2 --- Reactivity Studies --- p.45 / Chapter 2.3.3.3 --- Synthesis of[MCL1)3H] (M = Zr7 and Hf8) --- p.48 / Chapter 2.3.3.4 --- Reactivity Studies of Compound7 --- p.49 / Chapter 2.3.3.5 --- Physical Characterization of Compound 8 --- p.51 / Chapter 2.3.3.6 --- Molecular Structures of Compound 8 --- p.53 / Chapter 2.3.3.7 --- Synthesis of [Zr(L1)3Me] (9) --- p.57 / Chapter 2.3.3.8 --- Reactivity Studies of Compound 9 --- p.58 / Chapter 2.3.3.9 --- Physical Characterization of Compound 9 --- p.59 / Chapter 2.3.3.10 --- Molecular Structure of Compound 9 --- p.60 / Chapter 2.4 --- EXPERIMENTALS FOR CHAPTER 2 --- p.64 / Chapter 2.4.1 --- General Procedures --- p.64 / Chapter 2.4.2 --- Synthesis of Compounds --- p.65 / REFERENCES FOR CHAPTER 2 --- p.68 / Chapter CHAPTER 3. --- SYNTHESIS AND STRUCTURES OF VANADIUM(III) AMIDO AND BENZAMIDINATO COMPLEXES / Chapter 3.1 --- INTRODUCTION --- p.74 / Chapter 3.1.1 --- General Background --- p.74 / Chapter 3.1.2 --- A Brief Introduction on Metal Amidinates --- p.75 / Chapter 3.1.3 --- An Overview on Vanadium(III) Amides --- p.77 / Chapter 3.1.4 --- An Overview on Vanadium(III) Amidinates --- p.82 / Chapter 3.2 --- AIMS OF OUR STUDIES --- p.85 / Chapter 3.3 --- RESULTS AND DISCUSSION --- p.86 / Chapter 3.3.1 --- Synthesis and Structures of Dinuclear Vanadium(III) Amides --- p.86 / Chapter 3.3.1.1 --- Synthesis of[V(L1)2(μ~Cl)]2(10) --- p.86 / Chapter 3.3.1.2 --- Reactivity Studies --- p.88 / Chapter 3.3.1.3 --- Synthesis of [V(L1)2(μ-H)]2 (11) --- p.90 / Chapter 3.3.1.4 --- Physical Characterization of Compounds 10 and 11 --- p.90 / Chapter 3.3.1.5 --- Molecular Structures of Compounds 10 and 11 --- p.94 / Chapter 3.3.2 --- Synthesis and Structure of Mononuclear Vanadium(III) Benzamidinate --- p.102 / Chapter 3.3.2.1 --- "Synthesis of [Li(L2)(tmeda)] (13) (L2 = [PhC(NSiMe3) (NC6H3Me2-2, 6)])" --- p.102 / Chapter 3.3.2.2 --- Synthesis of [V(L2)2Cl] (14) and trans´ؤ[V(tmeda)2Cl2] (15) --- p.103 / Chapter 3.3.2.3 --- Reactivity Studies --- p.104 / Chapter 3.3.2.4 --- Physical Characterization of Compound 14 --- p.107 / Chapter 3.3.2.5 --- Molecular Structure of Compound 14 --- p.107 / Chapter 3.4 --- EXPERIMENTALS FOR CHAPTER 3 --- p.111 / Chapter 3.4.1 --- General Procedures --- p.111 / Chapter 3.4.2 --- Synthesis of Compounds --- p.112 / Chapter 3.5 --- REFERENCES FOR CHAPTER 3 --- p.115 / Chapter CHAPTER 4. --- SYNTHESIS AND STRUCTURES OF CHROMIUM AMIDO AND BENZAMIDINATO COMPLEXES / Chapter 4.1 --- INTRODUCTION --- p.122 / Chapter 4.1.1 --- General Background --- p.122 / Chapter 4.1.2 --- An Overview on Chromium(III) Amides --- p.122 / Chapter 4.1.3 --- An Overview on Chromium(II) Amidinates --- p.125 / Chapter 4.2 --- AIMS OF OUR STUDIES --- p.129 / Chapter 4.3 --- RESULTS AND DISCUSSION --- p.130 / Chapter 4.3.1 --- Synthesis and Structures of A Monomeric Chromium(III) Amide and A Chromium(II) Benzamidinate --- p.130 / Chapter 4.3.1.1 --- Synthesis of[Cr(L1)3] (16) --- p.130 / Chapter 4.3.1.2 --- Synthesis of [Cr(L2)2] (17) --- p.132 / Chapter 4.3.1.3 --- Physical Characterization of Compounds 16 and 17 --- p.133 / Chapter 4.3.1.4 --- Molecular Structures of Compounds 16 and 17 --- p.135 / Chapter 4.4 --- EXPERIMENT ALS FOR CHAPTER 4 --- p.141 / Chapter 4.4.1 --- General Procedures --- p.141 / Chapter 4.4.2 --- Synthesis of Compounds --- p.141 / Chapter 4.5 --- REFERENCES FOR CHAPTER 34 --- p.144 / APPENDIX 1 / Physical Measurements and X-Ray Crystallography --- p.147 / APPENDIX 2 / "Mass Spectra, 1'H and 13C{]H} NMR Spectra, and IR Spectra" --- p.148 / APPENDIX 3 --- p.172 / Table A-1. Selected crystallographic data for compounds 3-4 --- p.173 / Table A-2. Selected crystallographic data for compounds 8-9 --- p.174 / Table A-3. Selected crystallographic data for compounds 10-11 --- p.175 / Table A-4. Selected crystallographic data for compounds 14，16-17 --- p.176

Resumo: Neste trabalho novos complexos nitrosilos de rutênio (II) contendo bifosfinas foram obtidos e caracterizados. A série de complexos [RuCl3(NO)(P-P)] (1) foi utilizada como precursora na obtenção de compostos do tipo [Ru(pyS)2(P-P)] (2), P-P = dppe, c-dppen, dppp e dppb e [Ru(pyS)2(NO)(η1-P-PO)]PF6 (3), P-P = dppm e dppb; pyS = 2-mercaptopiridina, em rendimentos e pureza satisfatórios. Utilizou-se as técnicas usuais para caracterização dos complexos, entre elas: espectroscopias IV, UV/vis e RMN multinuclear (1H, 13C{1H} e 31P{1H}), voltametria cíclica, voltametria de pulso diferencial e análise elementar. A maioria dos compostos forneceu monocristais adequados para estudos por difração de raios-X. Os complexos do tipo (1) foram obtidos por rotas sintéticas já estabelecidas em nossos laboratórios. O inédito fac-[RuCl3(NO)(c-dppen)] foi isolado e caracterizado, tendo inclusive a estrutura cristalográfica resolvida. Este fato permitiu a realização de interessantes comparações deste com o isômero mer-[RuCl3(NO)(dppb)]. Adicionalmente, obtevese a estrutura cristalográfica do [RuCl3(NO)(c-dppen)] e realizou-se pela primeira vez ensaios eletroquímicos para toda a série (1) e experimentos de RMN multinuclear para o mer-[RuCl3(NO)(dppb)]. Assim, aproveita-se a oportunidade para algumas discussões adicionais, importantes para o melhor entendimento da série como um todo e para fins de comparação com os complexos derivados. Os produtos isolados nas reações com a pySH mostraram ser dependentes da bifosfina utilizada, já que o mesmo procedimento foi utilizado para obtenção dos derivados (2) e (3). A série (2) acima citada, com exceção do derivado com a c-dppen que é inédito, foi obtida anteriormente na literatura por rota de síntese diferente da aqui descrita. Apresentase a caracterização e discussão dos resultados ...(Resumo completo, clicar acesso eletrônico abaixo) / Abstract: In this work new nitrosyl complexes of ruthenium (II) containing diphosphines were obtained and characterized. The series of compounds [RuCl3(NO)(P-P)] (1) was used as the precursor to obtain compounds of the type [Ru(pyS)2(P-P)] (2), P-P = dppe, c-dppen, dppp and dppb and [Ru(pyS)2(NO)(η1-PPO)] PF6 (3), P-P = dppm and dppb; pyS = 2-mercaptopyridine, in acceptable yields and purity. Standard techniques were used for characterization of the compounds, among them: infrared, visible-UV and multinuclear NMR (1H, 13C{1H} and 31P{1H}) spectroscopies, cyclic voltammetry, pulse diferential voltammetry and elemental analysis. Most of the studied complexes supplied crystals suitable for X-ray crystal structure analysis. Compounds of type (1) were obtained by synthetic routes previously established in our laboratories. The unpublished fac-[RuCl3(NO)(dppb)] was isolated, characterized and had its crystallographic structure solved. This fact allowed interesting comparisons with the geometrical isomer mer-[RuCl3(NO)(dppb)]. In addition, the crystallographic structure of the [RuCl3(NO)(c-dppen)] was obtained and electrochemical characterization for all series (1) as well as multinuclear NMR experiments for the mer-[RuCl3(NO)(dppb)] were carried out for the first time. These studies offer us the opportunity for some additional discussions about the precursor complexes important to the comparisons with the results for the derivative compounds. The isolated products of the reactions with 2-mercaptopyridine ligand showed to be dependent on the diphosphine from the precursor, since the same procedure was used for obtaining derivatives (2) and (3). The series (2), mentioned above, was described previously in the literature, except for the c-dppen derivative, utilizing another synthetic route. The characterization and discussion ...(Complete abstract, click electronic access below) / Orientador: Alzir Azevedo Batista / Coorientador: Luiz Antônio A. de Oliveira / Mestre

L’objet de cette thèse est la convergence structure-fonction dans les systèmes complexes et ses applications aux systèmes vivants et aux systèmes technico-économiques. Après avoir défini la modularité et identifié les difficultés associées à sa définition, cette thèse formalise le concept de convergence structure-fonction dans les systèmes évolutifs et fonctionnels et montre son intérêt pour l’évolutivité et la robustesse de ces systèmes. Ensuite, elle applique ce concept à des problématiques réelles de systèmes évolutifs et fonctionnels en biologie et en économie afin d’illustrer son utilité. Ainsi, dans le cadre de la génomique, cette thèse montre que la longueur des opérons bactériens, qui sont à la fois des modules structurels et fonctionnels, est limitée du fait de contraintes dues à l’interaction des mécanismes de transcription et de réplication. Ensuite, elle fait l’hypothèse que la modularité structurelle des points chauds de recombinaison correspond au moins partiellement à la modularité fonctionnelle des gènes. Ceci permet de développer une nouvelle méthode d’analyse des études d’association génétique basée sur un découpage en régions géniques du génome dans le but de faciliter la compréhension du mécanisme fonctionnel de leur action sur le caractère étudié en analysant directement l’association de gènes ou de groupe de gènes avec ce caractère. Sur le plan structurel, les résultats sont d’une qualité comparable à ceux des méthodes classiques. En revanche, le découpage en régions devra encore être affiné afin d’obtenir une analyse fonctionnelle pleinement utile. Enfin, dans le cadre de la libéralisation du marché européen de l’électricité, la correspondance effective entre structure et fonction de chaque acteur issu de la restructuration fait supposer que le principe de convergence structure-fonction y est bien appliqué. Cependant, des difficultés subsistent avant de parvenir à mettre en place des relations structurelles permettant d’atteindre l’optimum souhaité. Celui-ci inclut des échanges d’énergie à l’origine des contraintes couplantes entre les acteurs. A partir de la théorie de la décomposition par les prix, nous proposons un cadre permettant de définir des tarifs propres à les faciliter, en particulier celles liant producteurs et transporteurs. En conclusion, cette thèse montre (a) la limite à la convergence structure-fonction que constitue la limite de la longueur des opérons bactériens, (b) la faisabilité de l’utilisation d’un découpage basé sur les limites de gènes afin d’analyser des études d’association génétique à grande échelle et (c) l’importance d’améliorer « la grande boucle » des relations entre producteurs et transporteurs d’électricité afin d’assurer l’optimisation conjointe des investissements en capacité de production et de transport. Elle synthétise l’ensemble de ces résultats dans le cadre conceptuel de la convergence structure-fonction qui postule que la modularité structurelle des systèmes évolutifs et fonctionnels tend à se superposer à leur modularité fonctionnelle afin de leur apporter robustesse et évolutivité. / The aim of this thesis is to investigate the structure-function convergence in complex systems by way of applications to living systems and technical-economical systems. Once having both defined modularity and identified the difficulties coupled to its core definition, this thesis formalizes the structure-function convergence in evolutive and functional systems and illustrates the interest of this concept with regard to the evolvability and robustness of these systems. Furthermore, this concept is applied to open questions in real biological and economic systems. In the field of genomics, this thesis establishes that the length of bacterial operons, which are structural and functional modules at the same time, is limited by the interactions of transcription and replication mechanisms. Then, this thesis make the hypothesis that the modular structure defined by recombination hotspots at least partially corresponds to the functional modularity defined by genes. This enables to develop a new method to analyse genetic association studies. It is based on a partition of the genome into bins with boundaries based on gene boundaries. This method renders easier the understanding of the functional mechanism of their action on the studied character. Indeed, it analyses directly the association of individual or group of genes with this character. On the structural level, results are of a quality comparable to those obtained obtained through standard methods. However, the gene based partition will need to be refined in order to obtain a fully useful functional analysis. Finally, when considering the opening-up of the European electricity market, the correspondence between structure and function of actors issued from the reorganization suggests that the structure-function convergence principle is correctly applied. However, the present structural relationships between actors prevent the system from reaching the desired optimality. This optimality includes energy exchanges which impose coupling constraints on the system. Thanks to the price decomposition theory, we propose a framework to define tariffs useful to improve such relationships, particularly those linking production and transmission operators. As a conclusion, this thesis shows (a) the limit of structure-function convergence implied by the length limit of bacterial operons, (b) the feasibility of a gene based bin analysis of genome-wide genetic association studies, (c) the importance of improving the relationships between production and transmission operators in order to assume a joint optimization of investments in production and transmission capacities. This thesis sums up these results in the conceptual framework of structure-function convergence, which postulates that the modular structure of evolutive and functional systems tend to superimpose their functional modularity in order to give them robustness and evolvability.

Les systèmes multi-agents sont caractérisés par le travail coopératif d'un ensemble d'agents autonomes, fonctionnant de manière décentralisée en vue de la réalisation d'un objectif global. Au sein de ces systèmes se produisent des phénomènes dits d'émergence, ou d'auto-organisation, par lesquels des structures ou des organisations particulières peuvent apparaître au niveau collectif qui n'étaient pas décrites de manière explicite au niveau individuel. Ainsi des fourmis qui s'organisent en files d'individus sans qu'aucune n'ait de représentation correspondant à la notion de "file". De par leurs interactions au niveau local, les agents produisent et maintiennent dynamiquement des structures au niveau global qui contraignent en retour l'activité de chacun des individus. Ces phénomènes sont fondamentaux dans l'étude des systèmes biologiques complexes mais sont pourtant très difficiles à formaliser car liés généralement à une interprétation en partie subjective d'un observateur extérieur au système. Le sujet proposé vise à aborder le problème du passage d'un niveau d'abstraction à un autre, ainsi que l'interaction, au sein d'un système, entre agents de différents niveaux, en combinant plusieurs approches complémentaires: une première approche concerne l'étude de formalismes adaptés à la représentation de phénomènes émergents. Cela passe notamment par la prise en compte de relations entre entités de différents niveaux d'abstraction, et par la prise en compte de comportements qui s'expriment différemment en fonction du niveau d'abstraction auquel l'entité est considérée. une deuxième approche qui s'appuiera sur la précédente concerne la détection automatique de phénomènes émergents. Pour ce faire, il sera nécessaire de développer des mécanismes permettant aux entités qui participent au système de détecter l'apparition de structures particulières (spatiales et/ou temporelles, statiques ou dynamiques) et de caractériser le passage d'un niveau d'abstraction donné au niveau supérieur. du fait de la très grande difficulté d'aborder le problème précédent dans toute sa généralité, nous prévoyons de développer une approche semi-interactive dans laquelle un observateur humain pourra avoir un rôle pour orienter le système vers la détection de structures particulières et leur caractérisation d'une manière particulière. Outre l'aide apportée au système, il s'agit d'orienter ce dernier vers la prise en compte d'abstractions a priori utiles et intéressantes. Cela passe notamment par la conception de modalités de visualisation et d'interaction adaptées à ce problème. ces différentes problématiques seront étudiées dans le cadre de plusieurs problèmes de simulation multi-agent pour la biologie. / Multi-agent systems are characterized by the cooperative work of a set of autonomous agents, operating in a decentralized manner with a view to achieving a goal. Within these systems produce phenomena known as emergence, or self-organization, in which structures or organizations may appear on a collective level that were not explicitly described at the individual level. Thus ants that are organized into files of individuals without having representation corresponding to the "file". Through their interactions at the local level, the agents produce and maintain structural dynamics at the global level which in turn constrain the activities of each individual. These phenomena are fundamental in the study of complex biological systems but are very difficult to formalize because usually related to a subjective interpretation of an observer outside the system. The subject is intended to address the problem of transition from one level of abstraction to another, and the interaction, within a system between officers of different levels, combining several complementary approaches: a first approach concerns study formalisms adapted to the representation of emergent phenomena. This includes taking account of relationships between entities of different levels of abstraction, and by taking behaviors that are expressed differently depending on the level of abstraction to which the entity is considered. a second approach which builds on the previous concerns the automatic detection of emergent phenomena. To do this, it will be necessary to develop mechanisms that allow entities that participate in the system to detect the emergence of structures (spatial and / or temporal, static or dynamic) and characterize the passage of a given level of abstraction to the next level. because of the great difficulty of dealing with the previous problem in all its generality, we plan to develop a semi-interactive approach in which a human observer may have a role to guide the system to detect structures and their characterization of a particular way. In addition to assisting the system, it is the guide to take into account a priori abstractions useful and interesting. This includes the design of procedures for display and interaction adapted to this problem. these issues will be explored in several issues of multi-agent simulation in biology.

by Cheng Pui Shan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2004. / Includes bibliographical references. / Abstracts in English and Chinese. / Abstract --- p.i / 摘要 --- p.iii / Acknowledgement --- p.iv / Table of Contents --- p.v / List of Compounds --- p.viii / Abbreviations --- p.xi / Chapter Chapter 1. --- A General introduction to Metal amides / Chapter 1.1 --- introduction / Chapter 1.1.1 --- General Background --- p.1 / Chapter 1.1.2 --- Metal Complexes with 2-Pyridyl Amido Ligands --- p.2 / Chapter 1.2 --- OBJECTIVES OF THIS WORK --- p.4 / Chapter 1.3 --- references for chapter1 --- p.5 / Chapter Chapter 2. --- Group 13 metal Amides / Chapter 2.1 --- GENERAL BACKGROUND --- p.8 / Chapter 2.1.1 --- Common Methods for the Preparation of Group 13 Metal Amides --- p.8 / Chapter 2.1.2 --- "An Overview on Aluminum(III), Gallium(III) and Indium(III) Amides" --- p.9 / Chapter 2.1.3 --- An Overview on Aluminum(III) Aryloxides --- p.15 / Chapter 2.2 --- aims of our studies --- p.18 / Chapter 2.3 --- results and discussion --- p.19 / Chapter 2.3.1 --- Preparation of [HN(SiButMe2)(2-C5H3N-6-Me)] (HL1) and Its Lithium Derivative [LiL1(TMEDA)] --- p.19 / Chapter 2.3.2 --- "Synthesis and Structures of Aluminum(III), Gallium(III) and Indium(III) Amides" / Chapter 2.3.2.1 --- "Synthesis of [MCl(L1)2] (M = Al 3, Ga 4) and [In(L1)3] (5)" --- p.20 / Chapter 2.3.2.2 --- Physical Characterization of Compounds 3-5 --- p.21 / Chapter 2.3.2.3 --- Molecular Structures of Compounds 3-5 --- p.24 / Chapter 2.3.3 --- Reactivity Studies --- p.35 / Chapter 2.3.3.1 --- Physical Characterization of Compounds 6 and7 --- p.38 / Chapter 2.3.3.2 --- Molecular Structures of Compounds 6 and7 --- p.39 / Chapter 2.4 --- EXPERIMENTALS FOR CHAPTER2 --- p.47 / Chapter 2.5 --- REFERENCES FOR CHAPTER2 --- p.52 / Chapter Chapter 3. --- A Silyl´ؤlinked diamine compound and its metal complexes / Chapter 3.1 --- A GENERAL INTRODUCTION TO DIAMINE COMPOUNDS --- p.59 / Chapter 3.2 --- A GENERAL INTRODUCTION TO MIXED ALKALI METAL AMIDES --- p.65 / Chapter 3.3 --- AIMS OF OUR STUDIES --- p.67 / Chapter 3.4 --- SYNTHESIS AND STRUCTURES OF [Me2Si{NH(2-Py)}2] AND THE CORRESPONDING ALKALI METAL AMIDES / Chapter 3.4.1 --- Synthesis and Structure of [Me2Si{NH(2-Py)}2] (HL2) (8) --- p.68 / Chapter 3.4.2 --- Synthesis and Structures of Alkali Metal Amides / Chapter i. --- Synthesis of Sodium Derivatives of8 --- p.74 / Chapter ii. --- Synthesis of a Mixed Alkali Metal Derivative of8 --- p.75 / Chapter iii. --- Attempted Metallation of 8 with KBun --- p.75 / Chapter iv. --- Physical Characterization --- p.77 / Chapter v. --- Molecular Structures --- p.80 / Chapter 3.5 --- synthesis and structure of the iron(ii) derivative [Fe(L2)Cl]2 / Chapter 3.5.1 --- An Overview on Iron(II) Amides --- p.95 / Chapter 3.5.2 --- Aims of Our Studies --- p.97 / Chapter 3.5.3 --- Synthesis and Structure of [FeCl(L2)]2 (14) / Chapter i. --- Synthesis and Characterization --- p.98 / Chapter ii. --- Molecular Structure --- p.99 / Chapter 3.6 --- EXPERIMENTALS FOR CHAPTER 3 --- p.102 / Chapter 3.7 --- REFERENCES FOR CHAPTER 3 --- p.106 / APPENDIX 1 / General Procedures and Physical Measurements --- p.110 / X-Ray Crystallography --- p.110 / APPENDIX 2 / Table A-1. Selected crystallographic data for compounds 3-5. --- p.113 / Table A-2. Selected crystallographic data for compounds 6´ؤ7. --- p.114 / Table A-3. Selected crystallographic data for compounds 8，10-11. --- p.115 / Table A-4. Selected crystallographic data for compounds 12-14. --- p.116