• Media type: E-Article
  • Title: Theoretical study on effect of substituent on aromaticity of tetrazole ring
  • Contributor: Yang, Chunhai; Li, Xue; Zhou, Ning; Chen, Bing; Dong, Huilong; Jin, Junxun; Hu, Xiuli; Huang, Tao; Shen, Lei; Yi, Jun; Wang, Quan; Ouyang, Dihua
  • Published: Canadian Science Publishing, 2023
  • Published in: Canadian Journal of Chemistry, 101 (2023) 10, Seite 781-789
  • Language: English
  • DOI: 10.1139/cjc-2023-0014
  • ISSN: 0008-4042; 1480-3291
  • Keywords: Organic Chemistry ; General Chemistry ; Catalysis
  • Origination:
  • Footnote:
  • Description: Tetrazole compounds are a category of energetic materials with great potential. Their stability is inherently related to their aromatics. On the basis of research in DFT at b3lyp/6–311** level on three compounds interested, viz. 5-amino-1 H-tetrazole, 5-carboxyl-1 H-tetrazole, and 2-methyl-5-carboxyl-tetrazole, their aromatic characters are extensively analyzed by virtue of different estimation method. Analyses show that these methods, Nucleus-independent Chemical Shift, iso-chemical shielding surface, adaptive natural density partitioning, π-electrons density, and localized orbital locator of π-electron density are efficient for substituted-tetrazole ring aromaticity estimation. Conclusion denotes that both substituent and substituted position can significantly affect the aromaticity of tetrazole ring of tetrazole compound. Among these given substituents, electro-withdrawing group -COOH significantly increases the aromaticity of the tetrazole rings due to the withdrawing to π-electrons thereof but electro-donating group -NH2 weakens the one of the tetrazole rings due to the donating to π-electrons thereof. But for 2-methyl-5-carboxyl-tetrazole, the aromaticity increasing of -COOH imposed on π-electrons of tetrazole ring thereof is partially balanced by the existence of the electron-donating group -CH3 at asymmetric meta-position of tetrazole ring. Consequently, the aromaticity order is 5-Carboxyl-1 H-tetrazole > 2-methyl-5-Carboxyl-tetrazole > 5-amino-1 H-tetrazole.