| Summary: | 博士 === 國立臺灣大學 === 化學研究所 === 100 === Metal porphyrins can act as important active site in the organism. Accordingly, the design of metal porphyrin complexes that are able to efficiently catalyze synthetic reactions is of great interest. We have synthesized a series of metalporphyrins (2d-g) with trifluoromethyl group and hydrophilic substitutes. Synthetic metalloporphyrins have been used in a variety of oxidation reactions as catalysts. Iron(III) porphyrin complex 2d was found to catalyze the oxidation of 1-ethylbenzene with NHPI as a co-catalyst. Ruthenium(II) porphyrin complex 2g can oxidize phenylmethanol in the presence of CuI under the basic condition. Benzaldehyde was obtained in low yield (20 %) by using the complex 2w as the catalyst. In the presence of urea or imidazole or related derivatives as additives, the selectivity of the product is achieved. In addition, the octachlorinated derivative of metal porphyrin ([FeCl(Cl8TPP)] and [RuCO(Cl8TPP)]) catalyze oxidation of cyclopropanol to the corresponding ketone and hydroxo in by molecular oxygen.
The second part of this thesis is researching the neutral tetradentate di(pyridyl)naphthyridine ligand (bpnp). Dicopper catalyst [Cu2(bpnp)(OH)(TFA)3]. was found to act as an efficient catalyst for the oxidative coupling of 2,6-di-substituted phenol to yield diphenoquinone, as well as of amination of aryl halides or dihalides. The dicopper complex was also applied to the oxidation of double bond, the coupling of phenylmethanethiol and the oxidation of furin. Dirhodium(II) complex Rh2(bpnp)(OAc)3)](OAc) can catalyze the reduction of double or triple bond and the oxidation of diol. The structure and electric effect of ligands (ppnp and bipypranp) is an important factor to increase the ratio of major product.
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