手性配位立体化学的创始、传承和发展

doi:10.12461/PKU.DXHX202405081

摘要/Abstract

摘要： 2024年是我们在厦门大学化学系开展cis-[CoBr (NH₃)(en)₂]Br₂的拆分和绝对不对称合成研究20周年，距配位化学创始人Alfred Werner于1911年成功拆分cis-[CoX (NH₃)(en)₂]X₂(X=Br^-、Cl^-)两个系列络合物已经113周年。为了纪念Werner及其团队对配位化学创始和发展的非凡贡献，本文首次通过详述cis-[CoX (NH₃)(en)₂]X₂的拆分(Alfred Werner携Victor Louis King和Ernst Scholze)和cis-[CoBr (NH₃)(en)₂]Br₂的绝对不对称合成(Kouichi Asakura)初创探究、后续进展以及相关研究，阐明手性八面体络合物的配位立体化学在科学发展史上的重要作用，并对cis-[CoBr (NH₃)(en)₂]Br₂的绝对不对称合成提出基于配位化学基本原理的“电子转移催化-结晶诱导”机理。

关键词: 配位化学, 立体化学, 八面体络合物, 手性, 拆分, 绝对不对称合成, 反应机理

Abstract: 2024 marks the 20th anniversary of our research on the resolution and absolute asymmetric synthesis of cis-[CoBr(NH₃)(en)₂]Br₂ in the department of chemistry at Xiamen University. It has been 113 years since the founder of coordination chemistry, Alfred Werner, successfully resoluted the two series of complexes cis-[CoX(NH₃)(en)₂]X₂ (X = Br^-, Cl^-) in 1911. In order to commemorate Werner and his team’s extraordinary contributions to the founding and development of coordination chemistry, this article for the first time elaborates on the initial exploration, subsequent progress, and related studies on the resolution (Alfred Werner with Victor Louis King and Ernst Scholze) of cis-[CoX(NH₃)(en)₂]X₂and the absolute asymmetric synthesis (Kouichi Asakura) of cis-[CoBr(NH₃)(en)₂]Br₂. It elucidates the important role of coordination stereochemistry of chiral octahedral complexes in the history of scientific development, and the “electron transfer catalysis-crystallization induction” mechanism based on the basic principles of coordination chemistry is proposed for the absolute asymmetric synthesis of cis-[CoBr(NH₃)(en)₂]Br₂.

Key words: Coordination chemistry, Stereochemistry, Octahedral complex, Chirality, Resolution, Absolute asymmetric synthesis, Reaction mechanism

方雪明, 陈雷奇, 王宪营, 丁冬冬, 南子昂, 张仕林, 林丽榕, 章慧. 手性配位立体化学的创始、传承和发展[J]. 大学化学, 2025, 40(1): 234-246.

Xueming Fang, Leiqi Chen, Xianying Wang, Dongdong Ding, Ziang Nan, Shilin Zhang, Lirong Lin, Hui Zhang. Creation, Inheritance and Development of Chiral Coordination Stereochemistry[J]. University Chemistry, 2025, 40(1): 234-246.

链接本文: https://www.dxhx.pku.edu.cn/CN/10.12461/PKU.DXHX202405081

https://www.dxhx.pku.edu.cn/CN/Y2025/V40/I1/234

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