金属卟啉仿生催化中的磁作用分子机理研究

Based on the porphyrin structure existing in the chlorophyl and heme, the transitional and lanthanon metalloporphyrins with full singal electron arrangement are designed and synthesized, and the biomimetic catalytic model for hydrocarbon oxidation over metalloporphyrins is built. The biomimetic catalysis installation with a variable maganetic field is set up, and is used to carry out the hydrocarbon oxidation catalyzed by metalloporphyrins. Based on our former finding that the biomimetic catalysis property of the metalloporphyrins was intensively influenced by the magnetic field, this project will farther search the rules that the maganetic field influence the catalytic property of metalloporphyrins for the hydrocarbon oxidation, and research the influence of the maganetic field on the stereochemistry and the environment factors existed in the biomimetic catalysis of metalloporphyrins, and analyze the relationship between the electron structures and the catalytic property of metalloporphyrins. This project can provide more information for the knowing of the mechanism in the enzyme-catalyzed reaction, and provide the more evidences to uncover the mystery between the geomaganetic field and the human.

基于自然界叶绿素和血红素活性中心的共同结构特征，设计并合成具有全充满单电子排布的过渡金属和稀土金属卟啉，建立金属卟啉仿生催化碳氢化合物氧化反应模型。设计并制造带可变磁场的反应装置来进行金属卟啉仿生催化碳氢化合物氧化反应。在以前发现磁性对金属卟啉仿生催化性能有特殊作用的基础上，进一步考察外加磁场对金属卟啉仿生催化反应性能的影响规律；探讨磁场对金属卟啉仿生催化反应中的立体化学和环境因素的影响；从金属卟啉电子结构分析磁场影响金属卟啉催化性能的规律。为了解酶催化反应机理提供更多的信息，为揭示地球磁场对人类生命作用的奥秘提供理论和实验依据．

合成了过渡金属铁、锰、钴、、镍、铜以及稀土金属的不同取代金属卟啉并进行了结构表征，重点研究了二价和三价钴卟啉以及稀土卟啉的合成控制和纯化方法；设计并制造了带可变磁场的金属卟啉仿生催化碳氢化合物氧化反应装置；以环己烷/PhIO作为仿生催化碳氢化合物氧化反应模型研究了所合成金属卟啉在磁场条件和非磁场条件下对环己烷氧化反应的仿生催化作用；考察了外加磁场对金属卟啉仿生催化反应性能的影响规律；探讨了金属卟啉仿生催化反应中金属原子结构对催化性能的影响。研究结果表明，外加磁场对稀土金属卟啉的仿生催化性能影响不大，而过渡金属卟啉中，外加磁场对铁卟啉的影响明显，对其他金属卟啉的影响不大。实验过程中还发现了三价铁卟啉对惰性铵离子氧化的温和催化作用以及锰卟啉催化的非端基炔烃氧化重排新反应。项目期间发表SCI论文27篇，包括2篇Chem Comm论文, 10篇JOC论文, 2篇Adv Synth & Catal论文；毕业研究生16名，其中博士研究生6名。