Citation: 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. doi: 10.6023/A20030084 shu

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

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

Corresponding author: Huang Rongyi, aqhuangry@hotmail.com Xu Heng, aqxuhengg@163.com
Received Date: 24 March 2020
Available Online: 14 May 2020
Fund Project: the National Natural Science Foundation of China 21975003Project supported by the National Natural Science Foundation of China (No. 21975003) and the Program for Innovative Research Team in Anqing Normal University

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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.
- metal catalysis,
- reaction mechanism,
- cadmium(Ⅱ) polymer,
- quantum chemical calculation,
- polynitrogen anion
1. [1]
  Demko, Z. P.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2110. doi: 10.1002/1521-3773(20020617)41:12<2110::AID-ANIE2110>3.0.CO;2-7
2. [2]
  Demko, Z. P.; Sharpless, K. B. Angew. Chem., Int. Ed. 2002, 41, 2113. doi: 10.1002/1521-3773(20020617)41:12<2113::AID-ANIE2113>3.0.CO;2-Q
3. [3]
  Wu, T.; Yi, B. H.; Li, D. Inorg. Chem. 2005, 44, 4130. doi: 10.1021/ic050063o
4. [4]
  Ye, Q.; Wang, X. S.; Zhao, H.; Xiong, R. G. Chem. Soc. Rew. 2005, 34, 208. doi: 10.1039/B407253G
5. [5]
  Chen, X. M.; Tong, M. L. Acc. Chem. Res. 2007, 40, 162. doi: 10.1021/ar068084p
6. [6]
  Li, J. R.; Tao, Y.; Yu, Q.; Bu, X. H. Chem. Commun. 2007, 1527.
7. [7]
  Zhao, H.; Qu, Z. R.; Ye, H. Y.; Xiong, R. G. Chem. Soc. Rev. 2008, 37, 84. doi: 10.1039/B616738C
8. [8]
  Shang, J.; Zhang, J.; Cui, Y.; Zhang, T.; Shu, Y.; Yang, L. Acta Chim. Sinica 2010, 68, 233 (in Chinese).
9. [9]
  Cantillo, D.; Gutmann, B.; Oliver Kappe, C. J. Am. Chem. Soc. 2011, 133, 4465. doi: 10.1021/ja109700b
10. [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. doi: 10.1039/c3ce27048c
11. [11]
  Li, X.; Cheng, L.; Fang, W.; Yang, G. Acta Chim. Sinica 2013, 71, 179 (in Chinese).
12. [12]
  Feng, Y.; Liu, X.; Duan, L.; Yang, Q.; Wei, Q.; Xie, G.; Chen, S.; Yang, X.; Gao, S. Dalton Trans. 2015, 44, 2333. doi: 10.1039/C4DT03131H
13. [13]
  Liu, X.; Gao, W.; Sun, P.; Su, Z.; Chen, S.; Wei, Q.; Xie, G.; Gao, S. Green Chem. 2015, 17, 831. doi: 10.1039/C4GC02184C
14. [14]
  Xiong, R. G.; Xue, X.; Zhao, H.; You, X. Z.; Abrahams, B. F.; Xue, Z. Angew. Chem., Int. Ed. 2002, 41, 3800. doi: 10.1002/1521-3773(20021018)41:20<3800::AID-ANIE3800>3.0.CO;2-3
15. [15]
  Jin, T.; Kitahara, F. K.; Kamijo, S.; Yamamoto, Y. Chem. Asian J. 2008, 3, 1575. doi: 10.1002/asia.200800085
16. [16]
  Himo, F.; Demko, Z. P.; Noodleman, L.; Sharpless, K. B. J. Am. Chem. Soc. 2003, 125, 9983. doi: 10.1021/ja030204q
17. [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. doi: 10.1002/anie.201505118
18. [18]
  Cantillo, D.; Gutmann, B.; Kappe, C. O. J. Am. Chem. Soc. 2011, 133, 4465. doi: 10.1021/ja109700b
19. [19]
  Huang, R. Y.; Zhang, C.; Yan, D.; Xiong, Z.; Xu, H.; Ren, X. M. RSC Adv. 2018, 8, 39929. doi: 10.1039/C8RA08486F
20. [20]
  Bader, R. F. W.; Essén, H. J. Chem. Phys. 1984, 80, 1943.
21. [21]
  Crèmer, D.; Kraka, E. Croat. Chem. Acta 1984, 57, 1259.
22. [22]
  Cremer, D.; Kraka, E. Angew. Chem., Int. Ed. 1984, 23, 67. doi: 10.1002/anie.198400671
23. [23]
  Espinosa, E.; Alkorta, I.; Elguero, J.; Molins, E. J. Chem. Phys. 2004, 387, 481.
24. [24]
  Ritter, J. J.; Minieri, P. P. J. Am. Chem. Soc. 1948, 70, 4045. doi: 10.1021/ja01192a022
25. [25]
  Ritter, J. J.; Kalish, J. J. Am. Chem. Soc. 1948, 70, 4048. doi: 10.1021/ja01192a023
26. [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. [27]
  Becke, A. D. Phys. Rev. A 1998, 38, 3098.
28. [28]
  Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785. doi: 10.1103/PhysRevB.37.785
29. [29]
  Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
30. [30]
  Andrae, D.; Häuerman, U.; Dolg, M.; Stoll, H.; Preu, H. Theor. Chim. Acta 1990, 77, 123. doi: 10.1007/BF01114537
31. [31]
  Bader, R. F. W. Atoms in Molecules, A Quantum Theory, Oxford University Press, Oxford, 1990.
32. [32]
  Boys, S. F.; Bernardi, F. Mol. Phys. 1970, 19, 553. doi: 10.1080/00268977000101561
33. [33]
  Lu, T.; Chen, F. W. J. Comp. Chem. 2012, 33, 580. doi: 10.1002/jcc.22885
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