| Summary: | 博士 === 國立中興大學 === 化學系所 === 98 === This thesis describes the preparation, characterization and catalytic investigation of novel palladium and aluminum complexes.
Chapter 1 describes a brief introduction of palladium-catalyzed cross-coupling reactions, including their applications, catalytic design and various catalytic systems.
Chapter 2 describes the preparation of novel four-membered ring diminie phosphine ligand, PhN=C(CMe2)(NPh)C=N(CH2)2PPh2 (128), and related phosphine oxide ligand, PhN=C(CMe2)(NPh)C=N(CH2)2P(O)Ph2 (129). Treatment of 128 or 129 with one equiv. Pd(OAc)2 in refluxed THF afforded an orthometallated [C, N, P] type palladacycle 130 or an acetate-bridged and orthometallated [C, N] type palladacycle 131, respectively. Reaction of 130 with excess of lithium chloride in methanol afforded an orthometallated [C, N, P] type palladacycle 132. The molecular structures are reported for compounds 130-132. The application of novel palladacycles to Suzuki and Heck reactions with aryl halide substrates was examined.
Chapter 3 describes preparations of a series of palladium anilido-oxazolinate complexes 179-189 from ligands, ortho-C6H4(NHAr)(4,4-dimethyl-2-oxazoline) (HNArOxa) [Ar = HNPhDiiPrOxa (173); HNPhTriMeOxa (174); HNPhOxa (175); HNPhOMeOxa (176); HNPhNMe2Oxa (178) and HNPhSMeOxa (179)] with Pd(OAc)2 give the palladium compounds, including bidentate η2-acetate mononuclear palladium complexes 179 and 180, an anilido-bridged dinuclear palladium complex 181, an acetate-bridged dinuclear complex 182, or tridentate mononuclear palladium complexes 183 and 184. The reactions of 179-184 with brine in acetone yielded palladium chloride complexes, including a chloride-bridged dinuclear palladium complex 185, an anilido-bridged dinuclear palladium complex 187, or tridentate mononuclear palladium complexes 186, 188 and 189. The molecular structures are reported for compounds 179-189. The application of novel palladium complexes to Suzuki and Heck reactions with aryl halide substrates was examined.
Chapter 4 describes a brief introduction of ring-opening polymerization, including their reaction types, applications, catalytic design and various catalytic systems.
Chapter 5 describes preparation of a series of aluminum anilido-pyrazolate complexes 333-337 from ligands, ortho-C6H4(NHAr)(1-pyrazole) (HNArOxa) [ Ar = HNPhPz (329); HNPhTriMePz (330); HNPhOMePz (331) and HNPhSMePz (332)] with AlMe3 in toluene gave the aluminum dimethyl complexes 333, 335-337 and an aluminum trimethyl complex 334, repetitively. The molecular structures are reported for compounds 334-336. Their catalytic activities toward the ring opening polymerization reaction of ε-caprolactone or lactide in the presence of BnOH were also under investigation.
Chapter 6 presents the general information of instrument and materials for the experiments in this thesis. The details of NMR spectroscopic data and X-ray structural data from this thesis are also present.
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