Studies on the Mechanism of the Transition Metal-Catalyzed Reaction of Organonitrile with Sodium Azide

doi:10.6023/A20030084

Acta Chimica Sinica ›› 2020, Vol. 78 ›› Issue (6): 565-571.DOI: 10.6023/A20030084 Previous Articles Next Articles

Article

过渡金属催化有机腈和叠氮酸钠反应机理的研究

黄荣谊, 沈琼, 张超, 张少勇, 徐衡

安庆师范大学化学化工学院功能配合物安徽省重点实验室安庆 246011

投稿日期:2020-03-24 发布日期:2020-05-14
通讯作者: 黄荣谊, 徐衡 E-mail:aqhuangry@hotmail.com;aqxuhengg@163.com
基金资助:
项目受国家自然科学基金（No.21975003）和安庆师范大学科研创新团队建设计划资助.

Studies on the Mechanism of the Transition Metal-Catalyzed Reaction of Organonitrile with Sodium Azide

Huang Rongyi, Shen Qiong, Zhang Chao, Zhang Shaoyong, Xu Heng

Anhui Key Laboratory of Functional Coordination Compounds and School of Chemistry and Chemical Engineering, Anqing Normal University, Anqing 246011

Received:2020-03-24 Published:2020-05-14
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21975003) and the Program for Innovative Research Team in Anqing Normal University.

1. Supporting Informaiton-A20030084.pdf(1990KB)

Abstract

The study on the reaction mechanism of organonitrile and sodium azide catalyzed by transition metals has always been a challenging and controversial task. Due to the difficulty in capturing the reaction intermediates, there is still no direct evidence to uncover the nature of the reaction. In this paper, the reaction mechanism has been explored by using a combining theoretical and experimental method. Based on the theoretical analysis of the stability of two types of intermediates (H₂O)₃M…N₃^- and (H₂O)₃M…NCCH₃ and the successful capture of two activated intermediates containing metal cadmium ions Cd₂(μ₃-N₃)(μ₃-OH)(μ₅-CHDA) (1) and Cd(μ₂-N₃)(μ₃-IBA) (2) (H₂CHDA=1,3-cycloadipic acid and HIBA=4-(imi-dazol-1-yl) benzoic acid), which were achieved under the hydrothermal conditions and characterized by single-crystal XRD analysis. For the first time, the experimental and theoretical results reveal that the transition metal ions activate the azide rather than the cyano group of nitriles. In addition, the results of both the electrostatic potential basins analysis of activated intermediates (H₂O)₃M…N₃^- and acetonitrile molecules obtained by the theoretical calculation and our recently reported experimental results reveal that the intermediates (H₂O)₃M…N₃^- can be used as electrophilic reagent. Its uncoordinated terminal N atom can attack the N atom of the cyano group of acetonitrile to undergo a nucleophilic addition reaction during the chemical reaction progress, and then it may undergo a[2+3] cycloaddition reaction to in-situ form tetrazole. Moreover, with the aid of water molecules, its adducts may also occur similar to the Ritter-like reaction to in-situ form polynitrogen anion. Our findings may open a novel field of the in-situ synthesis of polynitrogen compounds based on the transition metal-catalyzed reactions of organonitrile and azide.

Key words: metal catalysis, reaction mechanism, cadmium(II) polymer, quantum chemical calculation, polynitrogen anion

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Huang Rongyi, Shen Qiong, Zhang Chao, Zhang Shaoyong, Xu Heng. Studies on the Mechanism of the Transition Metal-Catalyzed Reaction of Organonitrile with Sodium Azide[J]. Acta Chimica Sinica, 2020, 78(6): 565-571.

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[1] Demko, Z. P.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2110.
[2] Demko, Z. P.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2113.
[3] Wu, T.; Yi, B. H.; Li, D. Inorg. Chem. 2005, 44, 4130.
[4] Ye, Q.; Wang, X. S.; Zhao, H.; Xiong, R. G. Chem. Soc. Rew. 2005, 34, 208.
[5] Chen, X. M.; Tong, M. L. Acc. Chem. Res. 2007, 40, 162.
[6] Li, J. R.; Tao, Y.; Yu, Q.; Bu, X. H. Chem. Commun. 2007, 1527.
[7] Zhao, H.; Qu, Z. R.; Ye, H. Y.; Xiong, R. G. Chem. Soc. Rev. 2008, 37, 84.
[8] Shang, J.; Zhang, J.; Cui, Y.; Zhang, T.; Shu, Y.; Yang, L. Acta Chim. Sinica 2010, 68, 233(in Chinese). (尚静, 张建国, 崔燕, 张同来, 舒远杰, 杨利, 化学学报, 2010, 68, 233.)
[9] Cantillo, D.; Gutmann, B.; Oliver Kappe, C. J. Am. Chem. Soc. 2011, 133, 4465.
[10] Wang, S. H.; Zheng, F. K.; Wu, M. F.; Liu, Z. F.; Chen, J.; Guo, G. C.; Wu, A. Q. CrystEngComm 2013, 15, 2616.
[11] Li, X.; Cheng, L.; Fang, W.; Yang, G. Acta Chim. Sinica 2013, 71, 179(in Chinese). (李新雄, 程琳, 方伟慧, 杨国昱, 化学学报, 2013, 71, 179.)
[12] Feng, Y.; Liu, X.; Duan, L.; Yang, Q.; Wei, Q.; Xie, G.; Chen, S.; Yang, X.; Gao, S. Dalton Trans. 2015, 44, 2333.
[13] Liu, X.; Gao, W.; Sun, P.; Su, Z.; Chen, S.; Wei, Q.; Xie, G.; Gao, S. Green Chem. 2015, 17, 831.
[14] Xiong, R. G.; Xue, X.; Zhao, H.; You, X. Z.; Abrahams, B. F.; Xue, Z. Angew. Chem., Int. Ed. 2002, 41, 3800.
[15] Jin, T.; Kitahara, F. K.; Kamijo, S.; Yamamoto, Y. Chem. Asian J. 2008, 3, 1575.
[16] Himo, F.; Demko, Z. P.; Noodleman, L.; Sharpless, K. B. J. Am. Chem. Soc. 2003, 125, 9983.
[17] Zhong, D. C.; Wen, Y. Q.; Deng, J. H.; Luo, X. Z.; Gong, Y. N.; Lu, T. B. Angew. Chem., Int. Ed. 2015, 54, 11795.
[18] Cantillo, D.; Gutmann, B.; Kappe, C. O. J. Am. Chem. Soc. 2011, 133, 4465.
[19] Huang, R. Y.; Zhang, C.; Yan, D.; Xiong, Z.; Xu, H.; Ren, X. M. RSC Adv. 2018, 8, 39929.
[20] Bader, R. F. W.; Essén, H. J. Chem. Phys. 1984, 80, 1943.
[21] Crèmer, D.; Kraka, E. Croat. Chem. Acta 1984, 57, 1259.
[22] Cremer, D.; Kraka, E. Angew. Chem., Int. Ed. 1984, 23, 67.
[23] Espinosa, E.; Alkorta, I.; Elguero, J.; Molins, E. J. Chem. Phys. 2004, 387, 481.
[24] Ritter, J. J.; Minieri, P. P. J. Am. Chem. Soc. 1948, 70, 4045.
[25] Ritter, J. J.; Kalish, J. J. Am. Chem. Soc. 1948, 70, 4048.
[26] Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Keith, T.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, O.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford, CT, 2013.
[27] Becke, A. D. Phys. Rev. A 1998, 38, 3098.
[28] Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
[29] Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
[30] Andrae, D.; Häuerman, U.; Dolg, M.; Stoll, H.; Preu, H. Theor. Chim. Acta 1990, 77, 123.
[31] Bader, R. F. W. Atoms in Molecules, A Quantum Theory, Oxford University Press, Oxford, 1990.
[32] Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553.
[33] Lu, T.; Chen, F. W. J. Comp. Chem. 2012, 33, 580.

过渡金属催化有机腈和叠氮酸钠反应机理的研究

Studies on the Mechanism of the Transition Metal-Catalyzed Reaction of Organonitrile with Sodium Azide

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