大家｜席振峰：金属有机、固氮、配位化学

关键词

Key word

氮气的活化与转化、金属有机化学、配位化学


简介

Introduction

席振峰，1963年生，河南省商丘市虞城县人，高中就读于虞城高中，1987-1989就读于南京大学和河南化学研究所过渡金属配位化学硕士研究生。

现为北京大学化学学院特聘教授、博士生导师、院士。

主要从事的科研方向是利用金属有机化合物研究高选择性有机合成新反应、新方法。致力于研究碳-氢键、碳-碳键以及碳-杂原子键的选择性切断与重组反应规律，探索新一代物质转化的途径。在《J. Am. Chem. Soc.》等著名杂志上发表过255余篇论文。

2015年评选为中国科学院院士。

2018年3月15日受聘于四川师范大学化学与材料科学学院名誉院长。

学习工作经历

Study & Word

  • 1999.07     北京大学化学学院教授
  • 1998.04     北京大学化学学院副教授
  • 1997-1998   日本北海道大学催化研究中心Takahashi教授课题组助手 (Assistant Professor)
  • 1996-1997   日本北海道大学催化研究中心Takahashi教授课题组博士后
  • 1996.10     获日本综合研究大学院大学(Sokendai)/日本分子科学研究所(IMS)理学博士学位
  • 1993-1996   日本分子科学研究所Takahashi教授课题组金属有机化学博士生
  • 1989-1992   河南化学研究所金斗满研究员课题组研究人员（助研）
  • 1989.06     获郑州大学配位化学硕士学位
  • 1987-1989   南京大学和河南化学研究所过渡金属配位化学硕士研究生
  • 1983-1987   河南化学研究所金斗满研究员课题组研究人员（实研）
  • 1983.07     获厦门大学化学系物理化学学士学位
  • 1979-1983   厦门大学化学系本科生

科研兴趣

Research

本研究室目前研究兴趣集中在如下两个方面。研究内容涉及金属有机化学、配位化学、光化学、电化学、有机合成化学及催化。
一、氮气的活化与转化。致力于实现温和条件下直接从氮气高效合成含氮有机化合物。
二、稀土金属有机化学（张文雄教授）。致力于发现新颖结构和P4的活化与转化。

科研成果

Research

一、双（多）金属有机合成试剂的合成、应用与机理：
二、金属有机杂环试剂的合成、应用与机理：
三、新型配体及其过渡金属配合物的合成、催化应用与机理：
四、常见惰性化学键碳-硅键、碳-氮键的催化活化、应用与机理：
五、稀土金属有机化合物的合成、应用与机理：
六、基于机理和金属有机活性中间体的碳二亚胺新化学：

代表论文

Papers

  1. J. Wei,* W.-X. Zhang, Z. Xi*, The Aromatic Dianion Metalloles, Chem. Sci. 2018, 9, 560-568.
  2. L. Liu, M. Zhu, H.-T. Yu, W.-X. Zhang,* Z. Xi*, Organocopper(III) Spiro Complexes: Synthesis, Structural Characterization, and Redox Transformation, J. Am. Chem. Soc. 2017, 139, 13688-13691.
  3. J. Li, J. Yin, C. Yu, W.-X. Zhang, Z. Xi*, Direct Transformation of N2 to N-Containing Organic Compounds, Acta Chim. Sinica 2017, 75, 733-743. (review)
  4. Y. Zhang, J. Wei, Y. Chi, X. Zhang, W.-X. Zhang,* Z. Xi,* Spiro Metalla-aromatics of Pd, Pt, and Rh: Synthesis and Characterization, J. Am. Chem. Soc. 2017, 139, 5039−5042.
  5. J. Wei, Y. Zhang, Y. Chi, L. Liu, W.-X. Zhang, Z. Xi*, Aromatic Dicupra[10]annulenes, J. Am. Chem. Soc. 2016, 138, 60-63.
  6. J. Wei, Y. Zhang, W.-X. Zhang, Z. Xi*, 1,3-Butadienyl Dianions as Non-innocent Ligands: Synthesis and Characterization of Aromatic Dilithio Rhodacycles, Angew. Chem. Int. Ed. 2015, 54, 9986-9990.
  7. S. Zhang, W.-X. Zhang, Z. Xi*, Semibullvalene and Diazasemibullvalene: Recent Advances in the Synthesis, Reaction Chemistry, and Synthetic Applications, Acc. Chem. Res. 2015, 48, 1823-1831.
  8. W.-X. Zhang, S. Zhang, Z. Xi*, Zirconocene and Si-Tethered Diynes: A Happy Match Directed toward Organometallic Chemistry and Organic Synthesis, Acc. Chem. Res. 2011, 44, 541-551.
  9. Z. Xi*, 1,4-Dilithio-1,3-dienes: Reaction and Synthetic Applications, Acc. Chem. Res. 2010, 43, 1342-1451.

最新进展

Progress

Outlook of nitrogen fixation by carbene
Chun-Hai Wang, Zhu-Bao Yin, Junnian Wei, Wen-Xiong Zhang, Zhenfeng Xi*. Tetrahedron, 2020, 76, 131703.
From the first N2-metal complex discovered in the 1960s to the borylene N2 complex reported very recently, chemists have been trying to activate N2 under milder conditions by investigating many approaches or strategies. Among them, carbene species has been considered a good choice to construct N–C bond to obtain N-containing organic compounds directly. Since the first glimpse of the N2 exchange of diazomethane, chemists have obtained a deeper understanding of the rebound reaction between carbene and N2. This review mainly summarizes the progress in the field of N2 fixation by using carbene species, both experimentally and theoretically. We believe this review will provide readers with an in-depth understanding of the state-of-the-art and perspectives of future research particularly in the use of carbene species for activation and transformation of N2 into N–C containing organic compounds.
文章链接
Direct transformation of dinitrogen: synthesis of N-containing organic compounds
via N−C bond formation
Ze-Jie Lv, Junnian Wei, Wen-Xiong Zhang, Ping Chen, Dehui Deng, Zhang-Jie Shi and Zhenfeng Xi*.
Natl. Sci. Rev, 2020, 7, 1564–1583.
N-containing organic compounds are of vital importance to lives. Practical synthesis of valuable N-containing organic compounds directly from dinitrogen (N2), not through ammonia (NH3), is a holy-grail in chemistry and chemical industry. An essential step for this transformation is the functionalization of the activated N2 units/ligands to generate N−C bonds. Pioneering works of transition metal-mediated direct conversion of N2 into organic compounds via N−C bond formation at metal-dinitrogen [N2-M] complexes have generated diversified coordination modes and laid the foundation of understanding for the N−C bond formation mechanism. This review summarizes those major achievements and is organized by the coordination modes of the [N2-M] complexes (end-on, side-on, end-on-side-on, etc.) that are involved in the N−C bond formation steps, and each part is arranged in terms of reaction types (N-alkylation, N-acylation, cycloaddition, insertion, etc.) between [N2-M] complexes and carbon-based substrates. Additionally, earlier works on one-pot synthesis of organic compounds from N2 via ill-defined intermediates are also briefed. Although almost all of the syntheses of N-containing organic compounds via direct transformation of N2 so far in the literature are realized in homogeneous stoichiometric thermochemical reaction systems and are discussed here in detail, the sporadically reported syntheses involving photochemical, electrochemical, heterogeneous thermo-catalytic reactions, if any, are also mentioned. This review aims to provide readers with an in-depth understanding of the state-of-the-art and perspectives of future research particularly in direct catalytic and efficient conversion of N2 into N-containing organic compounds under mild conditions, and to stimulate more research efforts to tackle this long-standing and grand scientific challenge.
文章链接
Synthesis and reactivity of asymmetric Cr(I) dinitrogen complexes supported by
cyclopentadienyl–phosphine ligands
Jiapeng Li, # Jianhao Yin, # Gao-Xiang Wang, # Zhu-Bao Yin, Wen-Xiong Zhang * and Zhenfeng Xi*.
（#共同一作）
Chem. Commun., 2019, 55, 9641.
Asymmetric trinuclear and dinuclear Cr(I) dinitrogen complexes bearing cyclopentadienyl–phosphine ligands were synthesized via reduction of their corresponding Cr(II) chloride complexes in the presence of N2. Oxidative addition reactions of single, double and triple bonds are found to take place on the low-valent Cr(I) centre.
文章链接
Scandium-Promoted Direct Conversion of Dinitrogen into Hydrazine Derivatives
via N−C Bond Formation
Ze-Jie Lv, Zhe Huang, Wen-Xiong Zhang,* and Zhenfeng Xi*. J. Am. Chem. Soc. 2019, 141, 8773−8777.
Direct conversion of dinitrogen (N2) into organic compounds, not through ammonia (NH3), is of great significance both fundamentally and practically. Here we report a highly efficient scandium-mediated synthetic cycle affording hydrazine derivatives (RMeN-NMeR′) directly from N2 and carbon-based electrophiles. The cycle includes three main steps: (i) reduction of a halogen-bridged discandium complex under N2 leading to a (N2)3--bridged discandium complex via a (N2)2-intermediate; (ii) treatment of the (N2)3- complex with methyl triflate (MeOTf), affording a (N2Me2)2--bridged discandium complex; and (iii) further reaction of the (N2Me2)2- complex with the carbon-based electrophile, producing the hydrazine derivative and regenerating the halide precursor. Furthermore, insertion of a CO molecule into one Sc-N bond in the (N2Me2)2--scandium complex was observed. Most notably, this is the first example of rare-earth metal-promoted direct conversion of N2 to organic compounds; the formation of C-N bonds by the reaction of these (N2)3- and (N2Me2)2- complexes with electrophiles represents the first case among all N2-metal complexes reported.
文章链接
Dinitrogen Functionalization Affording Chromium Hydrazido Complex
Jianhao Yin,# Jiapeng Li,# Gao-Xiang Wang,# Zhu-Bao Yin, Wen-Xiong Zhang,* and Zhenfeng Xi*. (#共同一作)
J. Am. Chem. Soc. 2019, 141, 4241-4247.
Dinitrogen fixation and functionalization mediated or catalyzed by transition-metal complexes have been a central research theme in chemistry. Although some successful examples have been reported in the literature, the search for novel bonding diversity of structurally well-defined transition metal-dinitrogen complexes and further transformation of coordinated N2 is still in great demand and of great challenge.
In this work, a series of trinuclear and dinuclear Cr(I)-N2 complexes bearing cyclopentadienyl-phosphine ligands were synthesized and characterized. Further reduction of the Cr(I)-N2 complexes generated anionic Cr(0)-N2 complexes, which could react with Me3SiCl to afford the first chromium hydrazido complex from N2 functionalization. These complexes were found to be effective catalysts for the transformation of N2 into N(SiMe3)3.
The isolation of the chromium hydrazido complex represented one of the key intermediates in the Cr-catalyzed N2 reduction cycle. This study should have a major scientific impact on the chemistry of transition-metal (Cr in particular) mediated or catalyzed dinitrogen fixation and transformation.
文章链接

人才培养

family

曾经在室人员：

教师：席振峰 李志平 张文雄

博士后（29人，包括短期博士后）：李志平，刘艳军，郑和根，索全伶，高国华，徐峰，钟振起，赵炳筠，闫红亮，吕健明，郭瑞云，高晔，范洪涛，王从洋，李国弢，张文雄，刘晓忠，侯学太，孔凡志，郑卫新，宋志毅，刘光臻，赵飞，王超，梁云，魏保生，刘亮，李嘉鹏，李楠

硕士研究生（3人）：李丕旭，宋秋玲，陈敬龙

博士研究生（35人）：赵长家，于涛，王从洋，李国弢，方红云，陆江，王志会，孙效华，毛国梁，王超，郁楠，胡乔舒，刘俊辉，刘澜涛，张慧君，王奇峰，李东阵，罗茜，王子涛，赵飞，孟天颢，张韶光，王杨，赵静，李恒，耿巍芝，周易，欧阳昆冰，魏俊年，徐凌，湛明，郝伟，迟樾，魏保生，刘亮

本科生（41人）：肖云海，张宜群，王华丽，管海荣，阎妮，王海琳，朱耀球，于涛，赵宇星，高卓，张新南，邓亮，颜珺，曹晓宇，陆江，王志会，袁健，王子涛，丛欢，孙晖，赵飞，郭向宇，张涵槊，刘迪，张韶光，李恒，师安，顾力，光洁，林辰，曹阳，王涵柳，李跃星，欧阳昆冰，魏俊年，迟樾，王羽琛，王涵，叶擎宇，陈天阳，杜帅靖

短期在室工作或学习人员（24人）：Martin Kotora，段征，原隆一郎 (Ryuichiro Hara)，王辉，北村正典 (Masanori Kitamura)，佐藤公彦(Kimihiko Sato)，周欣，蒲康之 (Yasuyuki Ura)，鲍峰玉，黄文迎，葛永辉，李石，村松彩子 (Ayako Muramatsu)，宫崎幹大 (Miyazaki Mikihiro)，谷向永，Raphael Sergent，Kevin Cheng，魏鹏辉，江新航，商翱，刘通，张璇，王连军，朱苗苗

研究室秘书（4人）：江莹，万原池，张梦华，陈洪培

以及目前在室人员：

席振峰，张文雄；李嘉鹏，李楠，郑煜；张永亮，马汪洋，杜山山，杨琪，殷剑昊，黄哲，俞超，严海涵，吕泽杰，王高翔，殷珠宝，胡静远；朱苗苗；申景航，柴正祺；陈洪培

评述

Discussion

席振峰老师自从1983年在厦门大学获得理学学士学位后，从事了几年工作；1987-1989年，在南京大学和河南化学研究所过渡金属配位化学从事研究工作，获得硕士学位，此后又工作了几年；1993-1996年，在日本分子科学研究所Takahashi教授课题组攻读金属有机化学博士，并获得博士学历；在日本从事了一年博士后、一年助理教授。1998年回国，在北京大学开始了独立课题研究，至今已有二十三年。他带领团队在固氮化学领域做出了杰出贡献，发现了“协同效应”在该领域的重要应用，培养了许多高层次的研究人员。
席老师在课题组十周年、二十周年庆上，说自己“愚钝，但是很幸运，坚持……”。此正所谓“古之成大事者，不惟有超世之才，亦必有坚韧不拔之志”。
我虽与席老师未曾谋面，却心有戚戚焉。祝席老师身体健康、事业顺利、科研不断取得突破进展。

参考资料

Reference

课题组网站：
https://www.chem.pku.edu.cn/zfxi/index.htm
https://www.chem.pku.edu.cn/xizf/revised/cyjs/ds/560903.htm
官网：
https://www.chem.pku.edu.cn/szll/zzjs/yjhxyjs1/89595.htm
百科：
https://baike.baidu.com/item/%E5%B8%AD%E6%8C%AF%E5%B3%B0/2928915?fr=aladdin
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