双核金属配合物的合成、表征及其仿生催化研究
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摘要
生物催化剂——金属酶是在特定的生物环境中，进行其它催化剂无可比拟的高效性、选择性和极度温和反应条件的催化反应。研究金属酶的结构与功能，合成它们的模拟物，探索它们在有机合成和工业生产中的应用，一直是人们追求的目标。经验表明，主攻点应为研究金属酶的活性中心内金属离子的配位环境，有目的地设计相应的催化体系，使其能反映反应活性中心的结构和周围的配位环境。由于天然的酶分子结构复杂，稳定性差，而小分子配合物可塑性强、易于了解酶的结构、功能及反应机理。所以酶的低分子量简单模型配合物的研究己成为生命科学和化学研究中最为活跃的课题之一，同时它对丰富配位化学、酶化学、仿生化学及其相关领域具有重大的学术价值。
双金属核广泛存在于自然界的一些生物酶的活性中心，如甲烷单加氧酶(MMO)、酪氨酸酶、血蓝蛋白和牛红血球超氧歧化酶等。因此，双核金属配合物作为金属酶的模型化合物正引起人们极大的兴趣。本文主要针对具有双铁核中心的甲烷单加氧酶及具有双铜核中心的血蓝蛋白、酪氨酸酶进行模拟。首先设计、合成了二个系列Fe_2、Cu_2四种新的具有不对称结构及具有手性特征的模型配合物，并运用元素分析、摩尔电导、红外、核磁共振、紫外可见、顺磁共振和循环伏安法等手段对其进行了较详细的表征。然后，通过模拟生物酶催化反应的条件，对上述配合物的仿生催化性能进行了评价。
本文第一章主要是对含双铁核的甲烷单加氧酶，从其来源、存在形式、组成、结构和催化机理等五个方面进行了详细讨论。其次，对含双核铜的具有可逆键合氧的血蓝蛋白及活化氧的酪氨酸酶，从结构及其催化氧化作用机理方面作以简单介绍。最后从双铁核、双核铜配合物的结构模拟和功能模拟两方面综述了它们的研究进展。
甲烷单加氧酶是甲烷利用菌中的重要酶系，它能够在温和条件下将甲烷为甲醇，其不仅有重大的理论意义而且具有广泛的应用价值。第二章主要是不对称的手性甲烷单加氧酶模型配合物的合成与表征。介绍了从基本原料对甲基苯酚出发通过Reimer-Tiemann(R-T)反应、氯甲基化、N-烷基化、水解等多步反应完成配体的合成，在配体相同的基础上通过改变桥联羧基链的长短合成了三种不同羧酸桥的配合物。通过名种图谱分析表明，所得配合物与
设计分子一致。根据对甲烷单加氧酶的研究文献调查发现，这种分子中含k
氧桥的双铁核配合物比以往的模型配合物更接近于天然的甲烷单加氧酶中
心结构。其中两个铁原子具有不等同的配位环境，且配合物分于是有一个出
L．氨基酸弓I入的手性碳，使该类配合物兼有手性。手性也是生物酶所具有的
特征。目前这类配合物尚未见文献报道。
由于大环配体为金属离子提供了一种规定的配位环境并对金属离子的
物理化学性质，如偶合效应、电磁、氧化还原性等产生显著影响，所以被广
泛作为模型物以模拟金属酶的结构与功能。在第三章我们设计、合成了一种
新型不对称大环双核铜配合物。它是由双核化试剂 2，6－二甲酚基A甲基苯酚
和二胺、手性氨基酸及金属盐缩合而成，通过一系列表征证明该配合物与设
计目标分子相符，与文献报道的大环配合物不同的是该配合物中心铜原子具
有不等同化学环境与几何环境，同时该分于也具有手性。都是极接近于血蓝
蛋白和酪氨酸酶活性中心双铜核的配位环境，也是文献中尚未见的新型配合
物。
在第四章我们进一步采用单氧源给体PhIO作氧化剂，在温和条件下，评
价了上述双金属配合物对苯乙烯环氧化反应的催化作用。结果表明双铁核模
型配合物的催化性能颇似甲烷单加氧酶，双铜核配合物也具有较好的催化活
性。该类反应无需共还原剂参与，对环境保护有很大的促进作用，同时这也
对解释反应机理和发展新型环氧化催化剂具有重要的意义。
Biocatalysts -enzymes are well known for their ability to carry out chemical reactions with high selectivity and high efficiency under ambient conditions. Chemists have long been engaged in studying on the correlation between the structure and function of enzymes, and in prospecting their use in organic synthesis and industrial product Though a lot of research we found the most important thing is to study the coordinate environment of metal in the active site of enzyme, minimize the correspond catalytic systems purposely. In order to simulate the immediate coordination environment of the metallobiosite, the coordination chemists use synthetic analogues derived from small molecular compounds which have more plasticity and simple structure than that of metallobiosite so a lot of low-molecular-weight coordination compounds were prepared . it is of both academic and industrial important.
Continuing interest in the design and synthesis of various types of binuclear complexes is mainly due to their potential application as models for binuclear metallobiosites such as methane monooxygenase, tyrosinase, haemocyanin et al. In this paper we describle some of our work aimed at mimicking the methane monooxygenase, tyrosinase and haemocyanin. Three diiron complexes and one binuclear copper were synthesized and well characterized by element analysis, molecular conductivity, IR, Uv-vis, 1H NMR, Electron Paramagnetic Resonance and cyclic voltammetric. The results show that the complexes all have asymmetry chiral structure and their coordination environment are similar to the correspond enzymes. Their catalytic properties in olefin epoxidation were investigated with iodosylbenzene as a terminal oxidant under mild condition.
The first chapter concerns the research progress of Methane monooxygenase (MMO) introducing the MMO's resource, existent form, component and catalytic mechanism then haemocyanin and tyrosinase were introduced in the aspects of their structure and functional mechanism. Lastly we reviewed the chemical mimic of the enzyme from structure mimic to functional mimic and its catalytic properties research.
Methane monooxygenase which catalyzes the conversion of methane to methanol under mild conditions remains a very interesting theoretical problem and also has important particular implications. In the second part, preparations and characterizations of three different bridged complexes models of MMO are reported .The ligand is obtained by Reimer-Tiemann reaction, Chloromethylation, N-alkation, hydroxylation, reduction reactions. In the synthetic procedure of complexes, we gained three different bridged complexes by changing carboxylate bridges. The structure of the complexes
closely resemble with other MMO-like systems. The compounds have not been reported in the literature.
The chemistry of macrocyclic binuclear complexes has been stimulated by a desire to mimic the active sites of some metalloenzymes to search appropriate systems for binding and activating small molecular, and to investigate the mutual influence of two metal centres on the electric, magnetic and redox properties of such systems. So the search for marocycle ligands mimicking the environment of the metals in haemocyanin tyrosinase has resulted in a tremendous upsurge. In the third chapter, the new type of binuclear copper complex was synthesized from dinucleating ligand (2,6-difbrmyl-4-methyl phenol) by reaction with diamine and L-amino acid, Compared with the reported complexes, the complexes is asymmetrical and chiral, the structure is similar to the active sites of haemocyanin , tyrosinase .
In the last chapter the complexes' catalytic activities of transferring oxygen atom from PhIO to olefins were tested. The results show that they all have good catalytic properties and are friendly to the environment.
双金属核广泛存在于自然界的一些生物酶的活性中心，如甲烷单加氧酶(MMO)、酪氨酸酶、血蓝蛋白和牛红血球超氧歧化酶等。因此，双核金属配合物作为金属酶的模型化合物正引起人们极大的兴趣。本文主要针对具有双铁核中心的甲烷单加氧酶及具有双铜核中心的血蓝蛋白、酪氨酸酶进行模拟。首先设计、合成了二个系列Fe_2、Cu_2四种新的具有不对称结构及具有手性特征的模型配合物，并运用元素分析、摩尔电导、红外、核磁共振、紫外可见、顺磁共振和循环伏安法等手段对其进行了较详细的表征。然后，通过模拟生物酶催化反应的条件，对上述配合物的仿生催化性能进行了评价。
本文第一章主要是对含双铁核的甲烷单加氧酶，从其来源、存在形式、组成、结构和催化机理等五个方面进行了详细讨论。其次，对含双核铜的具有可逆键合氧的血蓝蛋白及活化氧的酪氨酸酶，从结构及其催化氧化作用机理方面作以简单介绍。最后从双铁核、双核铜配合物的结构模拟和功能模拟两方面综述了它们的研究进展。
甲烷单加氧酶是甲烷利用菌中的重要酶系，它能够在温和条件下将甲烷为甲醇，其不仅有重大的理论意义而且具有广泛的应用价值。第二章主要是不对称的手性甲烷单加氧酶模型配合物的合成与表征。介绍了从基本原料对甲基苯酚出发通过Reimer-Tiemann(R-T)反应、氯甲基化、N-烷基化、水解等多步反应完成配体的合成，在配体相同的基础上通过改变桥联羧基链的长短合成了三种不同羧酸桥的配合物。通过名种图谱分析表明，所得配合物与
设计分子一致。根据对甲烷单加氧酶的研究文献调查发现，这种分子中含k
氧桥的双铁核配合物比以往的模型配合物更接近于天然的甲烷单加氧酶中
心结构。其中两个铁原子具有不等同的配位环境，且配合物分于是有一个出
L．氨基酸弓I入的手性碳，使该类配合物兼有手性。手性也是生物酶所具有的
特征。目前这类配合物尚未见文献报道。
由于大环配体为金属离子提供了一种规定的配位环境并对金属离子的
物理化学性质，如偶合效应、电磁、氧化还原性等产生显著影响，所以被广
泛作为模型物以模拟金属酶的结构与功能。在第三章我们设计、合成了一种
新型不对称大环双核铜配合物。它是由双核化试剂 2，6－二甲酚基A甲基苯酚
和二胺、手性氨基酸及金属盐缩合而成，通过一系列表征证明该配合物与设
计目标分子相符，与文献报道的大环配合物不同的是该配合物中心铜原子具
有不等同化学环境与几何环境，同时该分于也具有手性。都是极接近于血蓝
蛋白和酪氨酸酶活性中心双铜核的配位环境，也是文献中尚未见的新型配合
物。
在第四章我们进一步采用单氧源给体PhIO作氧化剂，在温和条件下，评
价了上述双金属配合物对苯乙烯环氧化反应的催化作用。结果表明双铁核模
型配合物的催化性能颇似甲烷单加氧酶，双铜核配合物也具有较好的催化活
性。该类反应无需共还原剂参与，对环境保护有很大的促进作用，同时这也
对解释反应机理和发展新型环氧化催化剂具有重要的意义。
Biocatalysts -enzymes are well known for their ability to carry out chemical reactions with high selectivity and high efficiency under ambient conditions. Chemists have long been engaged in studying on the correlation between the structure and function of enzymes, and in prospecting their use in organic synthesis and industrial product Though a lot of research we found the most important thing is to study the coordinate environment of metal in the active site of enzyme, minimize the correspond catalytic systems purposely. In order to simulate the immediate coordination environment of the metallobiosite, the coordination chemists use synthetic analogues derived from small molecular compounds which have more plasticity and simple structure than that of metallobiosite so a lot of low-molecular-weight coordination compounds were prepared . it is of both academic and industrial important.
Continuing interest in the design and synthesis of various types of binuclear complexes is mainly due to their potential application as models for binuclear metallobiosites such as methane monooxygenase, tyrosinase, haemocyanin et al. In this paper we describle some of our work aimed at mimicking the methane monooxygenase, tyrosinase and haemocyanin. Three diiron complexes and one binuclear copper were synthesized and well characterized by element analysis, molecular conductivity, IR, Uv-vis, 1H NMR, Electron Paramagnetic Resonance and cyclic voltammetric. The results show that the complexes all have asymmetry chiral structure and their coordination environment are similar to the correspond enzymes. Their catalytic properties in olefin epoxidation were investigated with iodosylbenzene as a terminal oxidant under mild condition.
The first chapter concerns the research progress of Methane monooxygenase (MMO) introducing the MMO's resource, existent form, component and catalytic mechanism then haemocyanin and tyrosinase were introduced in the aspects of their structure and functional mechanism. Lastly we reviewed the chemical mimic of the enzyme from structure mimic to functional mimic and its catalytic properties research.
Methane monooxygenase which catalyzes the conversion of methane to methanol under mild conditions remains a very interesting theoretical problem and also has important particular implications. In the second part, preparations and characterizations of three different bridged complexes models of MMO are reported .The ligand is obtained by Reimer-Tiemann reaction, Chloromethylation, N-alkation, hydroxylation, reduction reactions. In the synthetic procedure of complexes, we gained three different bridged complexes by changing carboxylate bridges. The structure of the complexes
closely resemble with other MMO-like systems. The compounds have not been reported in the literature.
The chemistry of macrocyclic binuclear complexes has been stimulated by a desire to mimic the active sites of some metalloenzymes to search appropriate systems for binding and activating small molecular, and to investigate the mutual influence of two metal centres on the electric, magnetic and redox properties of such systems. So the search for marocycle ligands mimicking the environment of the metals in haemocyanin tyrosinase has resulted in a tremendous upsurge. In the third chapter, the new type of binuclear copper complex was synthesized from dinucleating ligand (2,6-difbrmyl-4-methyl phenol) by reaction with diamine and L-amino acid, Compared with the reported complexes, the complexes is asymmetrical and chiral, the structure is similar to the active sites of haemocyanin , tyrosinase .
In the last chapter the complexes' catalytic activities of transferring oxygen atom from PhIO to olefins were tested. The results show that they all have good catalytic properties and are friendly to the environment.
引文
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