European Journal of Chemistry 2023, 14(1), 39-52 | doi: https://doi.org/10.5155/eurjchem.14.1.39-52.2340 | Get rights and content

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A corrected benzene nitration three-step mechanism derived by DFT calculation and MO theory


Hongchang Shi (1,*) orcid

(1) Department of Chemistry, Tsinghua University, Beijing 100084, China
(*) Corresponding Author

Received: 24 Aug 2022 | Revised: 26 Sep 2022 | Accepted: 02 Nov 2022 | Published: 31 Mar 2023 | Issue Date: March 2023

Abstract


Density-functional theory (DFT) calculations at the LC-wHPBE/6-311++G(d,p) level found that the textbook three-step nitration mechanism of benzene in mixed acids was seriously wrong. Step 1 of generating nitronium ion (NO2+) is not spontaneous, the NO2+ is generated by Lewis collision, and needs to overcome a barrier Ea = 18 or 22 kcal/mol in mixed acid or in nitric acid. Obtaining the Ea of the Lewis collision by quantum chemical calculations is a highlight of the study. The reaction system (NO2+ + H2O) + HSO4 or + NO3 or + nH2O (n ≥ 1) can make NO2+ spontaneously change to HNO3 through a poly(≥3)-molecular acidification. Sulfuric acid can greatly reduce [H2O] and increase [NO2+]. Therefore, the nitration rate in mixed acid is much faster than that in nitric acid. Step 2, C6H6 + NO2+, is an electrophilic addition, follows the transition state theory, and needs to overcome a low barrier, ΔE* = 7 kcal/mol. The product of Step 2 is the σ-complex C6H6-NO2+. The essence of the electrophilic addition is the transfer of HOMO-1 electrons of C6H6 to LUMO of NO2+. Step 3 is a spontaneous Lewis acid-base neutralization without any barrier, and generates the target product nitrobenzene C6H5NO2. NO2+ and σ-complex are the two active intermediates in nitration. The benzene nitration rate control step is not Step 2 of generating σ-complex, but is Step 1 to generate NO2+. The DFT calculation obtains the barriers Ea and ΔE*, the reaction heats ΔHσ and ΔHp of each step of the nitration, resulting in the total nitration reaction heat ΔH = -35 kcal/mol. It is consistent with the experimental ΔH = -34 kcal/mol. Based on the results, a corrected benzene nitration three-step mechanism proposed.


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Keywords


Nitration; σ-Complex; LC-wHPBE; Mixed acid; Nitronium ion; DFT calculation

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DOI: 10.5155/eurjchem.14.1.39-52.2340

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Institute of Physical Chemistry, Tsinghua University, China.

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Shi, H. Eur. J. Chem. 2023, 14(1), 39-52. doi:10.5155/eurjchem.14.1.39-52.2340
Shi, H. A corrected benzene nitration three-step mechanism derived by DFT calculation and MO theory. Eur. J. Chem. 2023, 14(1), 39-52. doi:10.5155/eurjchem.14.1.39-52.2340
Shi, H. (2023). A corrected benzene nitration three-step mechanism derived by DFT calculation and MO theory. European Journal of Chemistry, 14(1), 39-52. doi:10.5155/eurjchem.14.1.39-52.2340
Shi, Hongchang. "A corrected benzene nitration three-step mechanism derived by DFT calculation and MO theory." European Journal of Chemistry [Online], 14.1 (2023): 39-52. Web. 31 May. 2023
Shi, Hongchang. "A corrected benzene nitration three-step mechanism derived by DFT calculation and MO theory" European Journal of Chemistry [Online], Volume 14 Number 1 (31 March 2023)

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