报告人: Wonwoo Nam教授
韩国梨花女子大学
报告摘要:
Dioxygen is essential in life processes, and enzymes activate dioxygen to carry out a variety of biological reactions. One primary goal in biomimetic research is to elucidate structures of reactive intermediates and mechanistic details of dioxygen activation and oxygenation reactions occurring at the active sites of enzymes, by utilizing synthetic metal-oxygen complexes. A growing class of metal-oxygen complexes, such as metal–superoxo, –peroxo, –hydroperoxo, and –oxo species, have been isolated, characterized spectroscopically, and investigated in various oxygenation reactions. During the past decade, we have been studying the chemical and physical properties of various reactive intermediates in oxygenation reactions, such as high-valent iron(IV)- and manganes(V)-oxo complexes of heme and non-heme ligands in oxo-transfer and C-H activation reactions, non-heme metal-peroxo complexes in nucleophilic reactions, and non-heme metal-superoxo complexes in electrophilic reactions. The effects of supporting and axial ligands on structural and spectroscopic properties and reactivities of metal-oxygen adducts have been extensively investigated as well. In this presentation, I will present our recent results on the reactivities of various metal-oxygen intermediates in electrophilic and nucleophilic oxidation reactions. The synthesis and structural and spectroscopic characterization of mononuclear nonheme metal-dioxygen intermediates will be discussed as well.
Keywords: Bioinorganic Chemistry; Biomimetic Compound; Dioxygen Activation; Metal-Oxygen Intermediates
Reference:
[1] Cho, J.; Sarangi, R.; Nam, W. Acc. Chem. Res. 2012, 45, 1321.
[2] Cho, J.; Jeon, S.; Wilson, S. A.; Liu, L. V.; Kang, E. A.; Braymer, J. J.; Lim, M. H.; Hedman, B.; Hodgson, K. O.; Valentine, J. S.; Solomon, E. I.; Nam, W. Nature 2011, 478, 502.
[3] Fukuzumi, S.; Kishi, T.; Kotani, H.; Lee, Y.-M.; Nam, W. Nature Chem. 2011, 3, 38.
[4] Fukuzumi, S.; Morimoto, Y.; Kotani, H.; Naumov, P.; Lee, Y.-M.; Nam, W. Nature Chem. 2010, 2, 756.
[5] Cho, J.; Sarangi, R.; Annaraj, J.; Kim, S. Y.; Kubo, M.; Ogura, T.; Solomon, E. I.; Nam, W. Nature Chem. 2009, 1, 568.
[6] Nam, W. Acc. Chem. Res. 2007, 40, 465; Guest editorial in a special issue on “Dioxygen Activation by Metalloenzymes and Models”.
[7] Nam, W. Acc. Chem. Res. 2007, 40, 522.
[8] Bukowski, M. R.; Koehntop, K. D.; Stubna, A.; Bominaar, E. L.; Halfen, J. A.; Münck, E.; Nam, W.; Que, L., Jr. Science 2005, 310, 1000.
[9] Rohde, J.–U.; In, J.–H.; Lim, M. H.; Brennessel, W. W.; Bukowski, M. R.; Stubna, A.; Münck, E.; Nam, W.; Que, L., Jr. Science 2003, 299, 1037.
报告人简介:
Nam教授是国际生物无机化学领域非常有影响的学者,在氧活化及催化氧化、水氧化及人工光合作用、金属离子的荧光探针等研究方向上取得了非常重要的研究成果。近年来,他以单核及多核铁配合物为细胞色素c模型物,探讨了他们在烷烃等底物的催化氧化中的作用,发现并表征了一系列高价铁中间体的结构和性质。例如,他的课题组获得了第一个非血红素Fe(IV)=O配合物的晶体结构,并进行了光谱表征,该成果于2003年在《Science》上发表;他的课题组还获得了首例巯基结合态的非血红素Fe(IV)=O配合物结构,该化合物可以非常好的模拟细胞色素P450的活性中间体,成果于2005年在《Science》上发表;最近,他的课题组获得了首例非血红素铁(Ⅲ)-过氧化合物,并且通过多种谱学方法研究了它与铁(Ⅲ)氢过氧化合物、铁(IV)-氧化合物三者之间的转化关系,该成果于2011年在《Nature》上发表。迄今为止, Nam教授在Science,Nature,PANS,J. Am. Chem. Soc.,Angew. Chem. Int. Ed.等国际著名刊物上共发表SCI论文300余篇。他是《Chemical Science》副主编,南京大学兼职教授,香港大学的荣誉教授。
报告联系人:1101组 王永 (9763)