L'ouverture sélective de cycles aromatiques sur catalyseurs bifonctionnels peut en principe aboutir à une augmentation de l'indice de cétane des gazoles. Dans ce travail, nous nous sommes concentrés sur l'iridium supporté sur silice-alumine amorphe (ASA) comme catalyseur d'hydroconversion de la tétraline en présence de H2S à 250-350 °C dans un microréacteur continu sous pression (4 MPa). Une étude détaillée par analyse thermique et diffraction X in situ du processus de décomposition du précurseur acétylacétonate d'iridium a permis d'optimiser l'étape d'activation. Unesimple réduction sous H2 à 350 °C aboutit à des nanoparticules Ir finement dispersées (taille 1.4 ± 0.2nm). Le catalyseur Ir/ASA est stable et résiste à l'empoisonnement par le soufre, contrairement à Ir/SiO2 et Ir/Al2O3. Les principaux produits d'hydroconversion de la tétraline sont les produits d'hydrogénation (décalines) et les produits d'ouverture et de contraction de cycle (POCC). L'analyse par chromatographie en phase gazeuse bidimensionnelle (GC��GC-MS) montre que les POCC se répartissent en produits d'ouverture saturés et aromatiques, minoritaires, et en produits de contraction saturés et aromatiques, majoritaires. Les performances catalytiques de Ir/ASA ont pu être modifiéesvia des effets de support, d'alliage et de taille. Pour une composition Si:Al d'environ 0,5, l'acidité de Brönsted du support est maximale, ce qui conduit à une activité totale et une sélectivité en POCC maximales. D'autre part, l'activité augmente par ajout de palladium, et la sélectivité en POCC est maximale pour la composition Ir-Pd intermédiaire. Les analyses par TEM-EDX montrent que la teneur en Pd des nanoparticules augmente avec leur taille. Enfin, la sélectivité en POCC croîtconsidérablement avec la taille des particules, qui a été ajustée entre 2 et 8 nm par frittage thermiqueen atmosphère humide. Cela s'explique par une diminution du rapport entre les quantités de sitesmétalliques et de sites acides de Brönsted dans le cadre d'un mécanisme bifonctionnel.

Under the conditions of transfer hydrogenation employing ortho-cyclometallated iridium C,O-benzoate catalysts, selective silylallylation and CF₃-allylation were developed. In both cases, high levels of catalyst-directed enantioselectivity and diastereoselectivity were observed. Column chromatography was then tested as a new protocol to purify the iridium precatalyst; this single component precatalyst was proved to be more efficient to promote carbonyl crotylation reactions, both diastereo- and enantioselectivity were increased. Then, double asymmetric crotylation of 1,3-diols to deliver (pseudo-)C₂-symmetric adducts with exceptional level of enantioselectivity was devised. Implementation of this methodology and other hydrogenative C-C bond formations proved to be effective means for the preparation of two known polypropionate natural product fragments of C19-C25 of scytophycin C, C19-C27 of rifamycin S and the total synthesis of 6-deoxyerythronolide B. / text

A central tenant of organic synthesis is the construction of carbon-carbon bonds. One of the traditional methods for carrying out such transformations is that of carbonyl addition. Unfortunately, traditional carbonyl addition chemistry suffers various drawbacks: preactivation, moisture sensitivity, and the generation of stoichiometric organometallic waste. The research presented in this dissertation focuses on the development of methods that make use of nucleophile-electrophile pairs generated in situ via transfer hydrogenation, which allow the formation of carbonyl or imine addition products from the alcohol or amine oxidation level; streamlining the construction of complex molecules from simple, readily available starting materials. Additionally, studies toward the total synthesis of the fibrinogen receptor inhibitor tetrafibricin, utilizing the methods developed in catalytic carbon-carbon bond formation through the addition, transfer or removal of hydrogen, are presented. / text

Group 9 transition metal pincer complexes have shown tremendous utility in a variety of E-H (E = main group element) bond activation reactions. In an effort to access new types of highly reactive pincer-like transition metal complexes this research focuses on the development of new late metal complexes supported by tridentate bis(phosphino)silyl ligands of the type [?3-(2-R2PC6H4)2SiMe]- ([R-PSiP]; R = Cy, iPr). The incorporation of a strongly electron donating and highly trans-labilizing silyl group at the central anionic position may promote the formation of new coordinatively unsaturated compounds capable of enhanced reactivity. In this regard, the synthesis of coordinatively unsaturated Rh and Ir complexes supported by R-PSiP ligation and their ability to activate E-H bonds will be detailed. The synthesis of Cy-PSiP ligated Rh and Ir species and the ability to access the products of N–H bond oxidative addition with these species was investigated. Both [Cy-PSiP]Rh and [Cy-PSiP]Ir complexes were shown to form isolable complexes of the type [Cy-PSiP]M(H)(NHR) (M = Rh, R = aryl; M = Ir, R = H, aryl). However, attempts to generate such amido hydride complexes by N-H activation of the corresponding amine led to divergent reactivity, where adducts of the type [Cy-PSiP]Rh(NH2R) were obtained for Rh, while N-H bond oxidative addition was observed for Ir to form the targeted amido hydride complexes, including a rare example of ammonia N-H bond oxidative addition to form a monomeric, terminal parent amido complex that was crystallographically characterized. Due to the scarcity of transition metal complexes that are capable of N-H bond oxidative addition, a thorough investigation of the N-H bond activation mediated by [Cy-PSiP]Rh and Ir with various N-H containing substrates, including alkyl amines, hydrazine derivatives, and benzamides was initiated. Extension of this reactivity to the related diisopropylphosphino derivative [iPr-PSiP]IrI was also probed, as the resulting complexes were envisioned to be less susceptible to potential cyclometalation processes. Indeed, oxidative addition of primary alkyl amines, hydrazines, and benzamides was observed for [R-PSiP]Ir. These results comprise an unprecedented example of a metal complex that is capable of facile N-H bond activation in such a wide range of substrates, including challenging substrates such as ammonia and alkyl amines. A rare example of Rh-mediated N-H oxidative addition was also observed for the reaction of [Cy-PSiP]RhI with benzophenone hydrazone. The potential for these [R-PSiP]Ir(H)(NHR) complexes to insert unsaturated substrates was investigated, as the development of new pathways for the formation of C-N bonds via transition metal catalyzed N-H bond oxidative addition to a metal center followed by insertion of an alkene or alkyne into the M-N or M-H bond may provide a new pathway for accessing intermolecular amination reactions. Insertion chemistry attempts with various alkenes, alkynes, allenes, C=O and C?N containing compounds is described. Lastly, the synthesis of IrIII complexes of the type {[R-PSiP]IrR'}+X? (R = Cy, iPr; R’ = H, Me; X = OTf, BF4, B(C6F5)4) and their interactions with the C-H bonds of arenes and aldehydes, as well as, the Si-H bonds of hydrosilanes is detailed. The Si-H bond activation chemistry observed was typically influenced by the counter anion X. Thus, the more coordinating anions OTF and BF4 were shown to coordinate to and stabilize the highly electrophilic Si in transiently generated Ir silylene species.

Les travaux rapportés à l'intérieur de cette thèse traitent de la synthèse et de la caractérisation des propriétés optoélectronique de complexes hétéroleptiques d'iridium (III). Ces complexes organométalliques peuvent être utilisés entre autres comme luminophores à l'intérieur de cellules électrochimiques émettrices de lumière (LEEC) afin de produire des dispositifs d'éclairage ou d'affichage. Afin que ceux-ci soient commercialement viables, certaines propriétés des luminophores doivent être optimisées. La stratégie de recherche utilisée au cours de cette thèse se base sur une étude rigoureuse de type structure-propriété afin d'optimiser et de rationaliser les propriétés des luminophores synthétisés. Au cours du premier chapitre, des ligands auxiliaires de type 5,5'-diaryl-2,2'-bipyridine ont été synthétisés et ont été utilisés afin d'obtenir des complexes à la forme générale [(C^N)? Ir(N^N)](PF? ). Ces complexes ont démontrés des rendements quantiques supérieurs ainsi qu'une plus grande stabilité à l'intérieur de LEEC que ceux rapportés jusqu'à ce jour dans la littérature. Des hétérocycles non classiques, les aryl-1,2,3-triazoles ont été utilisés au chapitre 2 afin d'obtenir des ligands cyclométalliques nouveaux. Les complexes ainsi formés ont démontré une luminescence variant de jaune à bleu ciel et possèdent un état excité ³CT. Ces mêmes ligands ont été utilisés avec d'autres ligands auxiliaires électron-riches afin d'obtenir des complexes encore plus énergétiques et leurs propriétés ont été analysées au chapitre 3. Finalement, le chapitre 4 fait état des propriétés hors du commun d'un complexe neutre d'iridium comportant un ligand de type pyridyl-thiazinedioxide. Une étude complète des propriétés optoélectroniques a été effectuée afin de démontrer que ce complexe émettait des photons à partir de deux états radiatifs distincts, un cas très rare pour les complexes organométalliques de métaux de transition. [symboles non conformes]

This thesis aims to provide a detailed understanding of side-chain functionalized polymers as emissive materials for OLEDs. The syntheses and photophysical properties of these solution-processable materials as well as the effects of metal types, polymer backbones, chain lengths, spacer types and lengths, host types, and concentrations of the metal complexes on the emission properties and device performance will be dicussed. The polymers were functionalized with host materials along with the metal complexes to enhance the charge transport and to obtain energy transfer from the host to the complex. The physical and photophysical properties of the polymers were tuned by changing the backbone and the metal complex. Poly(norbornene)s, poly(cyclooctene)s, and poly(styrene)s were studied. The differences in the glass transition temperatures and PDIs of the polymers indicated that device performances might be affected by the polymer type due to the differences in the processability of the polymers. In addition to the backbone, it was found that device performance is dependent on various parameters such as molecular weight, metal loading, spacer type, and spacer length. In each case, it was found that the polymer backbone does not interfere with the basic photopysical properties of the metal complexes. The two main classes of metal complexes studied in this thesis are metalloquinolates and iridium complexes. It was shown that the emission properties of poly(cyclooctene)s containing 8-hydroxyquinolines in their side-chains could be altered by simply changing the metal. Green- and near IR-emitting polymers were synthesized by employing aluminum and ytterbium, respectively. On the other hand, for the iridium complexes, changes in color were achieved by varying the ligands. Iridium containing polymers with emission spectra that span the entire visible spectrum were synthesized by employing the appropriate ligands. It was demonstrated that OLEDs with high efficiencies can be fabricated by using these polymers as the emissive layer.

Transition-metal-catalyzed asymmetric hydrogenation is one of the most efficient, straightforward, and well-established methods for preparing enantiomerically enriched compounds. Over the past decades, significant progress has been made with iridium, rhodium and ruthenium complexes to asymmetric hydrogenate a selection of olefins, such as, α,β-unsaturated carboxylic acid derivatives, ketones, imines and phosphonates. Although these metals have been applied successfully in the hydrogenation of olefins, they differ in their substrate tolerance.  Ruthenium and rhodium based catalysts require a coordinating group in the vicinity of the C=C bond. However, iridium based catalysts do not require this coordinating group, hence, asymmetric hydrogenation with iridium catalysts has been widely used for both functionalized and unfunctionalized olefin substrates. This thesis focuses on expanding the substrate scope for asymmetric hydrogenation using chiral N,P-ligated iridium catalysts. Papers I and II investigate the asymmetric hydrogenation of prochiral N-heterocyclic compounds prepared by ring-closing metathesis using the iridium catalysts developed in our group.  These substrates are interesting as they bear resemblance to pharmaceutically active compounds and therefore have tremendous value in medicinal chemistry.  Excellent enantioselectivities, up to >99% ee and conversions were obtained. In papers III and IV we synthesized many unsaturated acyclic and cyclic sulfones with varying substitution patterns.  The sulfones were subjected to hydrogenation using our N,P-ligated iridium catalysts, producing the chiral sulfone products in high enantiomeric excess (up to 99% ee). This methodology was combined with the Ramberg-Bäcklund reaction, offering a novel route to chiral allylic and homoallylic compounds. In addition to obtaining these chiral compounds in good yields, no decrease in enantiomeric excess was observed after the Ramberg-Bäcklund reaction. This strategy has been applied in the preparation of the chiral building block for renin inhibitors.

Thesis (Ph.D.)--Tufts University, 1999. / Adviser: Samuel P. Kaunaves. Submitted to the Dept. of Chemistry. Includes bibliographical references (leaves 190). Access restricted to members of the Tufts University community. Also available via the World Wide Web;

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 119-130).

Thesis (Ph.D.)--Hong Kong University of Science and Technology, 2008. / Includes bibliographical references.