The development of a palladium-catalyzed intramolecular carboesterification of unactivated olefins is described. Olefin difunctionalization is a powerful tool for adding complexity to a molecule, and this formal [3+2] cycloaddition generates highly functionalized fused ring systems. Initially discovered by Dr. Yang Li in our group, it was found that when propiolic acids with a pendant terminal olefin were treated with 1 mol % Pd(MeCN)2Cl2, 3 equivalents of copper (II) chloride, and 3 equivalents of lithium chloride in acetonitrile at 50 °C, cyclization occurred in up to 90% yield. The optimization of this reaction and the extension to propiolamides and propargyl alcohols is described in this thesis. A mechanism involving a novel palladium-carboxylate species is proposed. Preliminary investigations into the synthesis of chiral sulfoxide pincer ligands are also described. The nucleophilic aromatic substitution of 1,3-dibromobenzene and 2,6-dichloropyridine with various thiols, followed by oxidation of the sulfides to sulfoxides is investigated as a route to the desired proligands.

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1. Benzene C-H Activation by Nickel(II) and Platinum(II) Complexes of Chelating Diarylamido Phosphine Ligands We have demonstrated an efficient intermolecular benzene C-H activation process mediated by Ni(II) complexes of ([Me-NP-iPr]Ni(L)(R)(L = Pyridine, 2,4-Lutidine, PMe3) and [iPr-NP-Ph]Ni(PMe3)(R) (R = Me, CH2SiMe3). When Lewis base is PMe3 or substituent is CH2SiMe3 more reactivity is observed. The amido diphosphine complexes [iPr-PNP]PtOTf effectively activate the benzene C-H bond in the presence of an appropriate Lewis base(NEt3 or DABCO). 2. Metal Complexes of Amido Phosphine Ligand Bearing Unsymmetric Donor Atom: Syntheses, Structures and Reactivities A series of [Ph-PNN]Ni(II)R (R = Me, Et, Ph, CH2Ph) complexes containing £]-hydrogen atoms have been prepared and characterizated. We have demonstrated an efficient intermolecular arene C-H activation process mediated by Ni(II) complexes of [Ph-PNN]NiEt at elevated temperature. A series of nickel(II) complexes featuring an unsupported, covalently bound p-donor ligand including anilide, phenolate, thiophenolate and tert-butoxide derivatives have been prepared and characterizated. Novel unsymmetric tridentate ligands (H[R-PNO], R = iPr, Ph) have been prepared and characterized. The reaction of [iPr-PNO]NiCl with Na/Hg in thf or ether at room temperature induced C-O bond activation followed by the generation of {[iPr-PNO]Ni}{[iPr-PNO*]NiMe}. 3. Amido Diphosphine Complexes of Cobalt: Syntheses, Structures and Reactivities A series of paramagnetic divalent cobalt complexes ([R-PNP]CoCl, R = iPr, Cy) supported by tridentate diarylamido phosphine ligands have been prepared and characterized. The diamagnetic monovalent cobalt-dinitrogen complexes ([R-PNP]Co(N2), R = iPr, Cy) are accessible from the reaction of [R-PNP]CoCl with LiHBEt3 in THF solution. The dinitrogen complex [Cy-PNP]Co(N2) reacts in THF with terminal alkynes, HC¡ÝCR, yielding vinylidene complexes ([Cy-PNP]Co=C=C(H)(R), R = Ph, SiMe3). The dinitrogen complex [Cy-PNP]Co(N2) and {[iPr-PNP]Co}2(£g-N2) reacts in THF with diphenylacetylene (PhC¡ÝCPh) yielding p complexes ([R-PNP]Co(h2-PhC¡ÝCPh), R = iPr, Cy). 4. Fluorinated Mono- and Diarylamido Complexes of Lithium and Group 4 Metals The synthesis of bis-ligand Group 4 metal complexes ([iPrAr-NF]2MCl2, M= Zr, Hf) are utilizing [iPrAr-NF]Li and MCl4(THF)2. The alkylation of [iPrAr-NF]2MCl2 with RMgCl (R= Me, iBu, PhCH2, Me3SiCH2) produced a series of group 4 metal complexes ([iPrAr-NF]2MR2, M= Zr, Hf) which are catalyst precursors for olefin polymerization. Deprotonation of H[iPr-NF] and H[Cy-NF] with n-BuLi in ethereal solutions at -35 ¢XC produced the lithium complexes {[iPr-NF]Li(solv)}2 (solv = THF, Et2O) and {[Cy-NF]Li(Et2O)}2, respectively. The metathetical reaction of [iPr-NF]Li(Et2O) with 1/3 equiv TiCl4(THF)2 in toluene solution produced the trianilide titanium complex [iPr-NF]3TiCl. A series of novel fluorinated bidentate (H[Mes-NP-RF], R = iPr, Ph) and tridentate ligands (H2[Mes-NPNF]) have been prepared and characterizated.

Thesis (Ph. D.)--University of Delaware, 2009. / Principal faculty advisor: Klaus H. Theopold, Dept. of Chemistry & Biochemistry. Includes bibliographical references.

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

Thèse de doctorat : Sciences de la vie et de la santé : Paris 12 : 2007. / Titre provenant de l'écran-titre. Bibliogr. 119 réf.

Reproduction de : Thèse doctorat : Chimie : Reims : 2007. / Titre provenant de l'écran titre. Bibliogr. f. 131-134.

Thèse doctorat : Chimie : Strasbourg 1 : 2006. / Titre provenant de l'écran-titre. Notes bibliogr.

Reproduction de : Thèse de doctorat : Chimie moléculaire : Toulouse 3 : 2007. / Titre provenant de l'écran-titre. Bibliogr. à la fin des chapitres.

Thèse de doctorat : Sciences du vivant : Strasbourg 1 : 2008. / Titre provenant de l'écran-titre. Bibliogr. 17 p.