手性配位立体化学的创始、传承和发展

doi:10.12461/PKU.DXHX202405081

Abstract

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

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.

References

[1] Werner, A. Z. Anorg. Chem. 1893, 3 (1), 267.
[2] Kauffman, G. B. Coordination Chemistry: A Century of Progress. American Chemical Society: Washington, DC, USA, 1994.
[3] 孟庆金, 戴安邦. 配位化学的创始与现代化. 北京: 高等教育出版社, 1998.
[4] 章慧, 等. 配位化学——原理与应用. 北京: 化学工业出版社, 2008.
[5] Werner, A.; Miolati, A. Z. Phys. Chem. 1893, 12U (1), 35.
[6] Werner, A.; Miolati, A. Z. Phys. Chem. 1894, 14U (1), 506.
[7] Werner, A.; Miolati, A. Z. Phys. Chem. 1896, 21U (1), 225.
[8] Kauffman, G. B. Isis 1970, 61 (2), 241.
[9] Berke, H. Educ. Quím. 2014, 25 (E1), 267.
[10] Werner, A.; Dubský, J. V. Ber. Dtsch. Chem. Ges. 1907, 40 (4), 4817.
[11] Werner, A.; King, V. L.; Scholze, E. Ber. Dtsch. Chem. Ges. 1911, 44 (2), 1887.
[12] King, V. L. J. Chem. Educ. 1942, 19 (7), 345.
[13] Kauffman, G. B. Inorganic Coordination Compounds. Heyden & Son Ltd.: London, UK, 1981; pp. 121-132.
[14] Ernst, K-H.; Wild, F. R. W. P.; Blacque, O.; Berke, H. Angew. Chem. Int. Ed. 2011, 50 (46), 10780.
[15] Kauffman, G. B.; Lindley, E. V. J. Chem. Educ. 1974, 51 (6), 424.
[16] Kauffman, G. B.; Lindey, E. V. 顺式-一溴一氨双(乙二胺)合钴(III)离子的拆解//无机合成. [美] Basolo, F. 主编. 张靓华, 等译. 申泮文校. 中译本, 第16卷, 合成28. 北京: 科学出版社, 1977: 101-106.
[17] Bernal, I.; Cetrullo, J.; Jackson, W. J. Coord. Chem. 1993, 28 (1), 89.
[18] Casadesus, M.; Coogan, M. P.; Davies, E.; Ooi, L. Inorg. Chim. Acta 2008, 361 (1), 63.
[19] 丁冬冬. 手性金属配合物的不对称合成和氧化还原手性光学开关应用初探[硕士学位论文]. 厦门: 厦门大学, 2011.
[20] Tobe, M. L.; Martin, D. F. 溴化顺式-一溴一氨双(乙二胺)合钴(III)、溴化顺式-和反式一水一氨双(乙二胺)合钴(III)和硝酸顺式-和反式一水一氨双(乙二胺)合钴(III)//无机合成. [美] Holtzclaw, H. F. 主编. 马维译, 申泮文校. 中译本, 第8卷, 合成51. 北京: 科学出版社, 1977: 161-164.
[21] 日本化学会编. 无机化合物合成手册. 曹惠民译. 第3卷. 北京: 化学工业出版社, 1988: 236.
[22] 颜文斌. 某些Co(III)/Fe(II)配合物间电子转移反应动力学研究[硕士学位论文]. 厦门: 厦门大学, 1994.
[23] 章慧. 某些Co(III)络合物的合成、拆分和[Co(edta)]^-的外界电子转移反应立体选择性研究[硕士学位论文]. 厦门: 厦门大学, 1995.
[24] 王宪营. Co(III)配合物的手性对称性破缺、合成及拆分机理研究[硕士学位论文]. 厦门: 厦门大学, 2006.
[25] 章慧, 王宪营, 陈雷奇, 方雪明, 高景星, 徐志固. 物理化学学报, 2006, 22 (5), 609.
[26] Asakura, K.; Kobayashi, K.; Mizusawa, Y.; Ozawa, S.; Osanai, S.; Yoshikawa, S. Physica D 1995, 84 (1-2), 72.
[27] Nakagawa, H.; Ohba, S.; Asakura, K.; Miura, T.; Tanaka, A.; Osanai, S. Acta Cryst. C 1997, 53 (2), 216.
[28] Knowles, W. S. Angew. Chem. Int. Ed. 2002, 41 (12), 1998.
[29] Werner, A. Z. Anorg. Chem. 1899, 21 (1), 145.
[30] Werner, A. Liebigs Ann. Chem. 1912, 386 (1-2), 1.
[31] Werner, A. On the Constitution and Configuration of Higher-Order Compounds. In Nobel Lectures in Chemistry (1901-1921); Elsevier Publishing Co.: New York, NY, USA, 1966; pp. 256-269.
[32] Werner, A. Ber. Dtsch. Chem. Ges. 1914, 47 (3), 3087.
[33] Werner, A. Helv. Chim. Acta 1918, 1 (1), 5.
[34] Kauffman, G. B. Part I: The Selected Papers of Alfred Werner. In Classics in Coordination Chemistry; Dover: New York, NY, USA, 1968.
[35] Kauffman, G. B. Isis 1975, 66 (1), 38.
[36] Bernal, I.; Kauffman, G. B. J. Chem. Educ. 1987, 64 (7), 604.
[37] 张清建. 大学化学, 1993, 8 (6), 52.
[38] 张清建. 自然辩证法通讯, 2000, 25 (1), 75.
[39] von Zelewsky, A. Chimia 2014, 68 (5), 297.
[40] Smirnoff, A. P. Helv. Chim. Acta 1920, 3 (1), 177.
[41] Drahoňovský, D.; von Zelewsky, A. Helv. Chim. Acta 2005, 88 (3), 496.
[42] Kudo, T.; Shimura, Y. Bull. Chem. Soc. Jpn. 1979, 52 (6), 1648.
[43] Spingler, B.; Scanavy-Grigorieff, M.; Werner, A.; Berke, H.; Lippard, S. J. Inorg. Chem. 2011, 40 (5), 1065.
[44] Blacque, O.; Berke, H. Chimia 2014, 68 (5), 299.
[45] Werner, A. Liebigs Ann. Chem. 1910, 375 (1), 1.
[46] Garçon, M.; Bakewell, C.; Sackman, G. A.; White, A. J. P.; Cooper, R. I.; Edwards, A. J.; Crimmin, M. R. Nature 2019, 574 (7778), 390.
[47] Jørgensen, S. M. J. Prakt. Che. 1890, 41 (1), 440.
[48] [美] A. 道格拉斯·斯通(A. Douglas Stone). 爱因斯坦与量子理论. 伍义生, 译. 北京: 机械工业出版社, 2019: 138-140, 173-174, 235-236.
[49] Bailar, J. C. Helv. Chim. Acta 1967, 50 (Supplement 1), 82-92.
[50] Werner, A.; Jantsch, G. Ber. Dtsch. Chem. Ges. 1907, 40 (4), 4426.
[51] Asakura, K.; Osanai, S.; Kondepudi, D. K. Chirality 2001, 13 (8), 435.
[52] Kobayashi, H.; Ohki, K.; Tsujikawa, I.; Osaki, K.; Uryû, N. Bull. Chem. Soc. Jpn. 1976, 49 (5), 1210.
[53] Asakura, K.; Kondepudi, D. K.; Martin, R. Chirality 1998, 10 (4), 343.
[54] Asakura, K.; Inoue, K.; Osanai, S.; Kondepudi, D. K. J. Coord. Chem. 1998, 46 (2), 159.
[55] Asakura, K.; Kurihara, K.; Ikumo, A.; Tanaka, A.; Miura, T.; Ozawa, T.; Kushibe, Y.; Osanai, S.; Kondepudi, D. K. Macromol. Symp. 2000, 160 (1), 7.
[56] Asakura, K.; Ikumo, A.; Kurihara, K.; Osanai, S.; Kondepudi, D. K. J. Phys. Chem. A 2000, 104 (12), 2689.
[57] Kondepudi, D. K.; Asakura, K. Acc. Chem. Res. 2001, 34 (12), 946.
[58] 方雪明, 章慧, 陈雷奇, 王宪营, 吴振奕, 董振荣. 大学化学, 2006, 21 (2), 48.
[59] Guo, F.; Casadesus, M.; Cheung, E. Y.; Coogan, M. P.; Harris, K. D. M. Chem. Commun. 2006, No. 17, 1854.
[60] 尤启东, 林国强主编. 手性药物——研究与应用. 北京: 化学工业出版社, 2004: 154, 157.
[61] 章慧, 吴振奕, 董振荣, 程大典. 实验二十三 [Co(en)₃]³⁺单一光学对映体的催化拆解制备//王尊本主编. 综合化学实验. 第2版. 北京: 科学出版社, 2007: 126-129.
[62] 徐志固编著. 现代配位化学. 北京: 化学工业出版社, 1987: 217.
[63] 徐志固, 章慧. 化学通报, 1984, 57 (12), 1.
[64] Zubieta, J. A.; Zuckerman, J. J. Chem. Eng. News 1976, 54 (15), 64.
[65] 孙章. 交叉融合的魅力: 跨学科文集. 上海: 同济大学出版社, 2023.

Creation, Inheritance and Development of Chiral Coordination Stereochemistry

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