金屬紫質與雙金屬錯合物之合成與其催化活性

Synthesis of Metalloporphyrins and Dimetal Di(pyridyl)naphthyridine Complexes and Their Catalytic Activities

廖倍偲(Bei-Sih Liao)

指導教授 ： 劉緒宗

國立臺灣大學/理學院/化學研究所/博士(2012年)

https://doi.org/10.6342/NTU.2012.00675

摘要

金屬紫質化合物是氧化還原酵素重要活性中心，因此模擬相關系統應用於有機物的合成成為注目的研究。論文中以合成tetraphenylporpphyrin (TPP) 上修飾-CF3基團之金屬紫質錯合物 [2d (FeCl)、2e (MnCl)、2f (RuCO)、2g (IrCl)及2aa (Co)] 與4-COOH之釕金屬紫質錯合物2w。這些錯合物做為氧化催化劑的測試，以探討紫質結構與金屬對於活性之影響。錯合物2d能於助催化劑NHPI下，使乙苯氧化生成苯甲醛；釕金屬錯合物2f與CuI於鹼性條件下，可將苯甲醇氧化為苯甲醛。但水溶性錯合物2w，對於乙苯之氧化反應只生成20 %的苯甲醛。此外，於紫質位置上修飾氯基團(Cl8TPP)所形成鐵[FeCl(Cl8TPP)]與釕[RuCO(Cl8TPP)]之錯合物也是合成目標物，由於氯基團使中心金屬較為缺電子，提昇其進行氧化之活性。氧氣下能使環丙醇開環氧化得到酮與羥酮兩種化合物，反應中添加尿素或咪唑及其衍生物進行軸向配位以改變產物之選擇性。
論文第二部分以雙金屬錯合物為主軸。[Cu2(CF3COO)4]與四芽基配位基bpnp可以形成之[Cu2(bpnp)(OH)(TFA)3]，其結構可由光譜與單晶結構確定。於氧氣下該錯合物催化2,6-di-substituted phenol之氧化耦合，得到diphenoquinone單一產物，此氧化耦合反應機制也作了探討。此雙銅錯合物也可催化鹵苯與氨水進行胺化反應， 得到高產率之芳香胺化合物，特別是雙胺化的反應更是優於其他催化劑。對於雙鍵氧化，硫醇化合物之耦合與furoin之氧化反應此雙銅錯合物也有很好的催化活性。另外，[Rh2(bpnp)(OAc)3)](OAc)能催化雙或三鍵之還原反應與二元醇之氧化反應。

關鍵字

金屬紫質 ； 氧化反應 ； 雙核錯合物 ； 耦合 ； 胺化

並列摘要

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.

並列關鍵字

metalporphyrin ； oxidation ； dinuclear complexes ； coupling ； amination

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