Au, Ching Chi. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2010. / Includes bibliographical references (leaves 83-89). / Abstracts in English and Chinese. / Table of contents --- p.i / Acknowledgements --- p.iii / Abbreviations --- p.iv / Abstract --- p.v / Chapter Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Importance of Transition Metal Amido Complexes --- p.1 / Chapter 1.1.1 --- Transition Metal Amido Complexes as Catalysts --- p.1 / Chapter 1.1.2 --- Transition Metal Amido Complexes as Reaction Intermediates --- p.2 / Chapter 1.2 --- Bonding Nature of Late Transition Metal Amido Complexes --- p.4 / Chapter 1.2.1 --- Theory of π Conflict --- p.5 / Chapter 1.2.2 --- E-C Approach --- p.7 / Chapter 1.3 --- Synthesis of Transition Metal Amido Complexes --- p.8 / Chapter 1.3.1 --- Transmetallation --- p.9 / Chapter 1.3.2 --- Deprotonation of Coordinated Amine --- p.10 / Chapter 1.3.3 --- Hydride Addition across Organic Azide --- p.11 / Chapter 1.4 --- Reactivity of Transition Metal Amido Complexes --- p.12 / Chapter 1.4.1 --- β-Elimination --- p.12 / Chapter 1.4.2 --- Insertion --- p.13 / Chapter 1.4.3 --- Reductive Elimination --- p.16 / Chapter 1.4.4 --- Bond Activation --- p.17 / Chapter 1.5 --- Structural Features of Rhodium Porphyrin Complexes --- p.18 / Chapter 1.6 --- Examples of Metalloporphyrin Complexes Containing Nitrogen Ligands --- p.19 / Chapter 1.7 --- Bond Activation by Rhodium Porphyrins --- p.21 / Chapter 1.8 --- Objectives of the Work --- p.23 / Chapter Chapter 2 --- Synthesis and Reactivity Studies of Rhodium Porphyrin Amido Complexes --- p.24 / Chapter 2.1 --- Synthesis of Porphyrin and Rhodium Porphyrin Chloride --- p.24 / Chapter 2.2 --- Synthesis of Rhodium Porphyrin Amido Complexes from Rhodium Porphyrin Chloride --- p.24 / Chapter 2.2.1 --- By Transmetallation with Lithium Amide --- p.25 / Chapter 2.2.2 --- By Base-promoted Ligand Substitution Using Rh(ttp)Cl --- p.27 / Chapter 2.2.2.1 --- Optimization of Reaction Conditions --- p.27 / Chapter 2.2.2.2 --- Substrate Scope --- p.31 / Chapter 2.3 --- X-ray Structure of Rh(ttp)NHS02Ph --- p.33 / Chapter 2.4 --- Bond Activation Chemistry of Rh(ttp)NHS02Ph --- p.36 / Chapter 2.5 --- Conclusion --- p.37 / Chapter Chapter 3 --- Reactivity Studies of Rh(ttp)NHS02Ph --- p.39 / Chapter 3.1 --- Thermal Reaction of Rh(ttp)NHS02Ph in Benzene-d6 --- p.39 / Chapter 3.2 --- Mechanistic Studies of the Conversion from Rh(ttp)NHS02Ph to [Rh(ttp)]2 --- p.41 / Chapter 3.2.1 --- Mechansim A (Hydrolysis of Rh(ttp)NHS02Ph) --- p.42 / Chapter 3.2.2 --- Mechanism B (Rh-N Bond Homolysis - (PhS02NH)2 Hydrolysis) --- p.44 / Chapter 3.2.3 --- Mechanism C (Rh-N Bond Homolysis - (PhS02NH)2 Nitrogen-Hydrogen Bond Activation) --- p.45 / Chapter 3.3 --- Discussions --- p.52 / Chapter 3.3.1 --- Estimation of Rhodium-Nitrogen Bond Dissociation Energy --- p.52 / Chapter 3.3.2 --- Effect of Excess PhS02NH2 in the Synthesis of Rh(ttp)NHS02Ph --- p.58 / Chapter 3.4 --- Conclusion --- p.58 / Chapter Chapter 4 --- Experimental Section --- p.60 / References --- p.83 / Appendix I X ray data --- p.90 / Appendix I List of Spectra --- p.96

Lai, Yin Man. / Thesis submitted in: November 2008. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2009. / Includes bibliographical references. / Abstracts in English and Chinese. / ACKNOWLEDGEMENT --- p.I / ABSTRACT --- p.II / 摘要 --- p.IV / ABBREVIATIONS --- p.V / LIST OF COMPOUNDS --- p.VI / TABLE OF CONTENTS --- p.IX / Chapter CHAPTER 1 --- A 2-PYRIDYL AMIDO LIGAND CONTAINING A PENTAFLUOROPHENYL SUBSTITUENT --- p.1 / Chapter 1. l --- General Background --- p.1 / Chapter 1.2 --- Examples of Amido Ligands --- p.3 / Chapter 1.3 --- An overview on Amido Ligands Containing Electron-withdrawing Substituents --- p.5 / Chapter 1.4 --- Objectives of This Work --- p.7 / Chapter 1.5 --- Results and Discussion --- p.8 / Chapter 1.5.1 --- Preparation of HLC6F5 (1) and its Potassium Derivatives --- p.8 / Chapter 1.5.2 --- Physical Characterization of Compounds 1-3 --- p.10 / Chapter 1.5.3 --- Molecular Structures of Compounds 2 and 3 --- p.13 / Chapter 1.6 --- Experimentals for Chapter 1 --- p.19 / Chapter 1.7 --- References for Chapter 1 --- p.22 / Chapter CHAPTER 2 --- "ZIRCONIUM(IV), VANADIUM(III) AND CHROMIUM(III) COMPLEXES DERIVED FROM THE [N(C6F5)(2-CsH3N-6-ME)] LIGAND" --- p.27 / Chapter 2.1 --- "An Overview on Zr(IV), V(III) and Cr(III) Complexes Supported by 2-Pyridyl Amido Ligands" --- p.27 / Chapter 2.2 --- Recent Results from our Group --- p.32 / Chapter 2.3 --- Objectives of this work --- p.33 / Chapter 2.4 --- "Synthesis and Structures of Tris(amido) Complexes of Zr(IV), V(III) and CR(III)" --- p.34 / Chapter 2.4.1 --- "Synthesis of [Zr(LC6F5)3(Cl) ´Ø C7H8] (4), V(LC6F5)3 (5) and [Cr(LC6F5)3] (6)" --- p.34 / Chapter 2.4.2 --- Molecular Structures of [Zr(LC6F5)3(Cl)´ØC7H8] (4)f and [Cr(LC6F5)3] (6) --- p.37 / Chapter 2.5 --- Experimentals for Chapter 2 --- p.43 / Chapter 2.6 --- References for Chapter 2 --- p.45 / Chapter CHAPTER 3 --- "MANGANESE(II), IRON(II), COBALT(II) AND NICKEL(II) COMPLEXES OF THE [N(C6F5)(2-C5H3N-6-ME)] LIGAND" --- p.49 / Chapter 3.1 --- A Brief Review on Amides of the Late Transition Metals --- p.49 / Chapter 3.2 --- Examples of Late Transition Metal Complexes Supported by 2-Pyridyl Amido Ligands --- p.51 / Chapter 3.3 --- Objectives of our studies --- p.53 / Chapter 3.4 --- "Synthesis and Structures of Bis(amido) Complexes of Mn(II), Fe(II), Co(II) and NI(II)" --- p.54 / Chapter 3.4.1 --- "Synthesis of [M(LC6F5)2(tmeda)] (M = Mn (7), Fe (8), Co (9), Ni (10)]" --- p.54 / Chapter 3.4.2 --- Molecular Structures of Complexes 7-10 --- p.57 / Chapter 3.5 --- "Synthesis, Structure and Reactivity of a Mono(amido) Fe(II) Complex" --- p.61 / Chapter 3.5.1 --- Synthesis of [Fe(LC6F5)(CI)(tmeda)](11) --- p.61 / Chapter 3.5.2 --- Physical Characterization of Compound 11 --- p.62 / Chapter 3.5.3 --- Molecular Structures of Compound 11 --- p.62 / Chapter 3.5.4 --- Reactivity Studies of [Fe(LC6F5)(Cl)(tmeda)] (11) --- p.66 / Chapter 3.6 --- Synthesis of Fe(III) Tri(amido) Complex --- p.69 / Chapter 3.7 --- Experimentals for Chapter 3 --- p.70 / Chapter 3.8 --- References for Chapter 3 --- p.73 / Chapter CHAPTER 4 --- SUMMARY OF THE PRESENT RESEARCH WORK --- p.75 / TABLE OF APPENDIX --- p.79 / "General Procedures, Physical Measurements and X-Ray Structural Analysis" --- p.80 / 1HNMR of HCC6F5(1) --- p.82 / 13CNMR of HLC6F5(1) --- p.83 / 19FNMR of HLC6F5(1) --- p.84 / 1HNMR of [K(LC6F5)(tmeda)]2 (2) --- p.85 / 13CNMR OF [K(LC6F5)(tmeda)]2 (2)) --- p.86 / 19FNMR of [K(LC6F5)(TMEDA)]2 (2)) --- p.87 / 1HNMR of [K(LC6F5)(thf)2]2 (3) --- p.88 / 13CNMR of [K(LC6F5)(thf)2]2 (3) --- p.89 / 19FNMR OF [K(LC6F5)(THF)2]2 (3) --- p.90 / 1HNMR of Zr(LC6F5)3(Cl).(C7H8)] (4) --- p.91 / Selected crystallographic data of complexes 2 and 3 --- p.94 / Selected crystallographic data of complexes 4 and 6 --- p.95 / Selected crystallographic data of complexes 7 and 8 --- p.96 / Selected crystallographic data of complexes 9 and 10 --- p.97 / Selected crystallographic data of complex 11 --- p.98

En aquest treball s'han abordat tres objectius, tots ells relacionats amb la reacció d'hidroformilació i en la seva aplicació a la síntesi de productes d'alt valor afegit.El primer dels objectius ha estat la síntesi de tres lligands ditioacetat quirals a partir de l'L-(-)-lactat d'etil i diols bicíclics, que en algun cas incorporaven un centre atropoisomèric, per a ser emprats en la reacció d'hidroformilació enantioselectiva catalitzada per complexos tiolat de rodi o bé en altres reaccions asimètriques. Els ditioacetats han pogut ser preparats però no de forma enantiomèricament pura, ja que s'ha observat una racemització del carboni estereogènic clàssic en la darrera de les cinc etapes previstes per la síntesi d'aquests compostos. En aquesta darrera etapa, la basicitat de l'anió tioacetat usat en la substitució nucleofílica dels productes ditosilats ha estat suficient per abstreure el protó a-carbonilic. No s'han trobat precedents d'una reacció similar amb aquest anió. El segon objectiu del treball ha estat la hidroformilació diastereoselectiva de tres trans-N-1-propeniltartarimides homoquirals. La ruta emprada per sintetitzar-les consisteix, en primer lloc, en la condensació de l'N-al·lilamina i l'àcid L-(-)-tartàric per obtenir l'N?al·liltartarimida. L'esterificació dels grups OH d'aquesta amb els anhídrids apropiats permet obtenir les N-al·liltartarimides funcionalitzades amb grups CH3COO-, (CH3)3COO- i PhCOO-. Finalment, la isomerització d'aquestes imides permet sintetitzar les trans-N-1-propeniltartarimides. Els precedents bibliogràfics indiquen que la isomerització d'imides és una reacció complicada, ja que sovint requereix quantitats elevades de catalitzador així com condicions de reacció dràstiques. En aquest treball s'han assajat diferents complexos metàl·lics de rodi i de ruteni com a catalitzadors d'isomerització. Els millors resultats s'obtenen utilitzant el complex RuClH(CO)(PPh3)3 (1% molar). S'assoleixen conversions properes al 90% en dues hores de reacció amb una regioselectivitat en l'isòmer trans del 90%. Aquests valors representen els millors resultats reportats fins al moment en aquest tipus de reacció. La hidroformilació de les trans-N-1-propeniltartarimides sintetitzades s'ha dut a terme amb catalitzadors de rodi no quirals amb la intenció d'obtenir els aldehids de manera diastereoselectiva. Els resultats obtinguts indiquen que és la naturalesa del substrat la que controla la formació de l'alquil complex i que l'estructura del catalitzador no influeix, de forma determinant, en la selectivitat. Per altra banda, no s'han observat en cap cas excessos diastereoisomèrics superiors al 10%, fet que indica que els diferents substituents no tenen un efecte clar sobre l'estereoselectivitat de la reacció.El tercer i darrer objectiu ha estat l'obtenció de l'N-acetil-2-pirrolina a partir de l'N-al·lilacetamida mitjançant la reacció d'hidroformilació. Aquest heterocicle nitrogenat pot usar-se com a buillding-block en la síntesi de diferents molècules amb activitat biològica, especialment alcaloides. La hidroformilació de l'N-al·lilacetamida s'ha portat a terme emprant catalitzadors de rodi i les difosfines Bisbi i Xantphos, i el difosfit tert-butil Biphephos com a co-catalitzadors. Amb el sistema Rh/Xantphos s'obtenen quimio- i regioselectivitats superiors al 90% en l'aldehid lineal o els seus derivats. La ciclació intramolecular del 2-acetamidobutanal, producte majoritari de la reacció d'hidroformilació, i la posterior deshidratació de l'alcohol resultant, permet obtenir l'N-acetil-2-pirrolina a partir de l'N?al·lilacetamida mitjançant un procés one pot amb una excel·lent economia atòmica. S'ha estudiat en profunditat la ciclació i posterior deshidratació. Així s'ha determinat que catalitzadors àcids de tipus Brönsted provoquen l'aparició de productes de doble condensació no desitjats i que el millor catalitzador per aquestes reaccions és el tamís molecular de 3 Å finament polvoritzat i assistit per una destil·lació en continu de l'azeòtrop toluè/aigua. Amb aquest mètode s'ha pogut obtenir el producte desitjat a partir de l'N?al·lilacetamida, CO, H2 i un 0.0002% de Rh amb un rendiment del 41%. / Three main goals were set at the beginning of this work, all of them related with the hydroformylation reaction and its application in the synthesis of fine chemicals.The first goal is the synthesis of three chiral ditioacetate ligands coming from the L?(-)-ethyl lactate and bicyclic diols, that in some cases contain an atropoisomeric centre. These ligands could be used in the enantioselective hydroformylation of olefins catalysed by rhodium complexes or in other asymmetric reactions. The ditioacetates were prepared but not enantiomerically pure, because of the racemization of the "classical" estereogenic centre in the last of the five steps of the synthetic pathway designed. In this last step, the basicity of the tioacetate anion used in the nucleophilic substitution of the corresponding ditosilate intermediates was enough to abstract the a?carbonilic hydrogen. As far as we know, there is no precedent of such a reaction with this anion.The second goal of this work is the diastereoselective hydroformylation of three homochiral trans-N-1-propenyltartarimides. The synthetic pathway consists, first of all, in the condensation of the N-allylamine and the L-(-)-tartaric acid to obtain the N?allyltartarimide. The esterification of the OH groups of this imide with the suitable anhydrides allows the synthesis of the corresponding N-allyltartarimides functionalised with the CH3COO-, (CH3)3COO- and PhCOO- groups. Finally, the isomerization of these imides leads to the trans-N-1-propenyltartarimides. The literature indicates that imide isomerization is a difficult reaction, usually it requires high levels of catalyst and heavy reaction conditions. In this work a number of rhodium and ruthenium complexes has been tested as catalysts. The best result were found using RuClH(CO)(PPh3)3 (1% molar). It is possible to reach yields up to 90% in two hours of reaction with a regioselectivity in the trans isomer up to 90%. As far as we know that results represent the best ones ever reported in such a reaction. The hydroformylation of the trans-N-1-propenyltartarimides has been done using non-chiral rhodium complexes as catalysts with the aim of obtaining the aldehydes in a diastereoselective way. The results obtained indicate that the nature of the substrate is controlling the alkyl complex formation during hydroformylation and that there is not any effect of the catalyst in the selectivity. Moreover, diastereomeric excess in the aldehydes formation does not exceed 10%, which indicates that there is not a clear effect of the substrate nature in the stereoselectivity of the reaction. The third and last goal of this work is the synthesis of N-acetyl-2-pyrroline through the hydroformylation of N-allylacetamide. This heterocycle containing nitrogen can be used as building-block for the synthesis of a number of molecules with biological activity, specially alkaloids. The hydroformylation of N-allylacetamide was attempted using rhodium catalysts and diphosphines (Bisbi and Xantphos) or diphosphites (tert-butil Biphephos) as co-catalysts. With the catalytic system Rh/Xantphos, chimio- and regioselectivities exceeding 90% in the linear aldehyde or their derivatives are obtained. 2-acetamidobutanal is the major product of the hydroformylation reaction, it cycles in an intramolecular way to obtain the corresponding alcohol, the dehydration of which leads to the N-acetyl-2-pyrroline in a one-pot process with an excellent atomic economy. The cycle formation and the dehydration reaction of the alcohol has been deeply investigated. It has been found that Brönsted catalysts promote double condensation products formation which are undesirable. After a number of tests the best catalyst for the one-pot reaction referred above is 3 Å molecular sieves finely powdered and assisted by a continuous distillation of the toluene/water azeotrop. According to this method it is possible to obtain N-acetyl-2-pyrroline from N-allylacetamide, CO, H2 and a 0.0002% of rhodium with a global yield of 41%.

Thesis (Ph. D.)--University of North Texas, May, 2009. / Title from title page display. Includes bibliographical references.

Reproduction de : Thèse doctorat : Chimie : Reims : 2006. / Titre provenant de l'écran titre. Bibliogr. f. 203-220.

Thesis (Honors)--College of William and Mary, 2009. / Includes bibliographical references (leaf 60). Also available via the World Wide Web.

Thesis (Ph. D.)--Hong Kong University of Science and Technology, 2003. / Includes bibliographical references (leaves 196-207). Also available in electronic version. Access restricted to campus users.

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