Theoretical Study of the Hydrogen Abstraction of Substituted Phenols by Nitrogen Dioxide as a Source of HONO. Shenghur, A., Weber, K., H., Nguyen, N., Sontising, W., & Tao, F. The journal of physical chemistry. A, 10, 2014. ![Theoretical Study of the Hydrogen Abstraction of Substituted Phenols by Nitrogen Dioxide as a Source of HONO. [pdf]](https://bibbase.org/img/filetypes/pdf.svg "pdf")
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Website abstract bibtex The mild yet promiscuous reactions of nitrogen dioxide and phenolic derivatives have been explored with density functional theory calculations. The anhydrous reaction is found to occur via four distinct pathways with both proton coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms available. While the parent reaction with unsubstituted phenol is found to be insignificant in the gas phase, electron donating groups in the ortho- and para- positions facilitate the reduction of nitrogen dioxide by electronically stabilizing the product phenoxy radical. Hydrogen bonding groups in the ortho- position may additionally stabilize the nascent resonantly stabilized radical product, thus enhancing the reaction. Catechol (ortho-hydroxy phenol) has a predicted overall free energy change G0 = -0.8 kcal mol-1 and electronic activation energy Ea = 7.0 kcal mol-1. Free amines at the ortho- and para- positions have ΔG0 = -3.8 and -1.5 kcal mol-1 and Ea = 2.3 and 2.1 kcal mol-1, respectively. When protonated, however, amino substituents do not contribute to the production of nitrous acid. Conversely, the strongly deactivating carboxy group when deprotonated is predicted to undergo a barrierless reduction of nitrogen dioxide when at the para position (ΔG0 = -4.24 kcal mol-1). Hammett constants produce a linear correlation with bond dissociation energy (BDE) demonstrating that the BDE is the main parameter controlling the dark abstraction reaction. The implications for atmospheric chemistry and ground level nitrous acid production are discussed.
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title = {Theoretical Study of the Hydrogen Abstraction of Substituted Phenols by Nitrogen Dioxide as a Source of HONO.},
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abstract = {The mild yet promiscuous reactions of nitrogen dioxide and phenolic derivatives have been explored with density functional theory calculations. The anhydrous reaction is found to occur via four distinct pathways with both proton coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms available. While the parent reaction with unsubstituted phenol is found to be insignificant in the gas phase, electron donating groups in the ortho- and para- positions facilitate the reduction of nitrogen dioxide by electronically stabilizing the product phenoxy radical. Hydrogen bonding groups in the ortho- position may additionally stabilize the nascent resonantly stabilized radical product, thus enhancing the reaction. Catechol (ortho-hydroxy phenol) has a predicted overall free energy change G0 = -0.8 kcal mol-1 and electronic activation energy Ea = 7.0 kcal mol-1. Free amines at the ortho- and para- positions have ΔG0 = -3.8 and -1.5 kcal mol-1 and Ea = 2.3 and 2.1 kcal mol-1, respectively. When protonated, however, amino substituents do not contribute to the production of nitrous acid. Conversely, the strongly deactivating carboxy group when deprotonated is predicted to undergo a barrierless reduction of nitrogen dioxide when at the para position (ΔG0 = -4.24 kcal mol-1). Hammett constants produce a linear correlation with bond dissociation energy (BDE) demonstrating that the BDE is the main parameter controlling the dark abstraction reaction. The implications for atmospheric chemistry and ground level nitrous acid production are discussed.},
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author = {Shenghur, Abraham and Weber, Kevin Howard and Nguyen, Nhan and Sontising, Watit and Tao, Fu-ming},
journal = {The journal of physical chemistry. A},
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The anhydrous reaction is found to occur via four distinct pathways with both proton coupled electron transfer (PCET) and hydrogen atom transfer (HAT) mechanisms available. While the parent reaction with unsubstituted phenol is found to be insignificant in the gas phase, electron donating groups in the ortho- and para- positions facilitate the reduction of nitrogen dioxide by electronically stabilizing the product phenoxy radical. Hydrogen bonding groups in the ortho- position may additionally stabilize the nascent resonantly stabilized radical product, thus enhancing the reaction. Catechol (ortho-hydroxy phenol) has a predicted overall free energy change G0 = -0.8 kcal mol-1 and electronic activation energy Ea = 7.0 kcal mol-1. Free amines at the ortho- and para- positions have ΔG0 = -3.8 and -1.5 kcal mol-1 and Ea = 2.3 and 2.1 kcal mol-1, respectively. When protonated, however, amino substituents do not contribute to the production of nitrous acid. Conversely, the strongly deactivating carboxy group when deprotonated is predicted to undergo a barrierless reduction of nitrogen dioxide when at the para position (ΔG0 = -4.24 kcal mol-1). Hammett constants produce a linear correlation with bond dissociation energy (BDE) demonstrating that the BDE is the main parameter controlling the dark abstraction reaction. The implications for atmospheric chemistry and ground level nitrous acid production are discussed.","bibtype":"article","author":"Shenghur, Abraham and Weber, Kevin Howard and Nguyen, Nhan and Sontising, Watit and Tao, Fu-ming","journal":"The journal of physical chemistry. 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