Here, the energetics of the regioselective mononitration of 9,10-BN-naphthalene with acetyl nitrate (H3C2NO4) were modeled with ab initio simulations in the gas phase and an acetonitrile solvent. The single-electron-transfer (SET) nitration mechanism leading to a σ-complex and a single-step nitration mechanism were modeled. The energy barrier for the single-step mechanism was lower than that for the SET mechanism in the gas phase. However, the two are much more energetically competitive in the solvent. The σ-complex was found to be unstable in the gas phase owing to the interaction with the counterion. Using the single-step mechanism, the carbon site 1 nearest boron had the lowest activation energy for nitration of 22.6 kcal/mol, while site 3 had the second lowest barrier of 24.6 kcal/mol. Finally, details on the molecular structures at intermediate and transition states as well as charges in different configurations are discussed.
Steele, Brad A., et al. "Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Naphthalene with Acetyl Nitrate in the Gas Phase." Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, vol. 126, no. 31, Aug. 2022. https://doi.org/10.1021/acs.jpca.2c02124
Steele, Brad A., Zhang, Mao-Xi, & Kuo, I-Feng W. (2022). Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Naphthalene with Acetyl Nitrate in the Gas Phase. Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, 126(31). https://doi.org/10.1021/acs.jpca.2c02124
Steele, Brad A., Zhang, Mao-Xi, and Kuo, I-Feng W., "Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Naphthalene with Acetyl Nitrate in the Gas Phase," Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory 126, no. 31 (2022), https://doi.org/10.1021/acs.jpca.2c02124
@article{osti_1884635,
author = {Steele, Brad A. and Zhang, Mao-Xi and Kuo, I-Feng W.},
title = {Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Naphthalene with Acetyl Nitrate in the Gas Phase},
annote = {Here, the energetics of the regioselective mononitration of 9,10-BN-naphthalene with acetyl nitrate (H3C2NO4) were modeled with ab initio simulations in the gas phase and an acetonitrile solvent. The single-electron-transfer (SET) nitration mechanism leading to a σ-complex and a single-step nitration mechanism were modeled. The energy barrier for the single-step mechanism was lower than that for the SET mechanism in the gas phase. However, the two are much more energetically competitive in the solvent. The σ-complex was found to be unstable in the gas phase owing to the interaction with the counterion. Using the single-step mechanism, the carbon site 1 nearest boron had the lowest activation energy for nitration of 22.6 kcal/mol, while site 3 had the second lowest barrier of 24.6 kcal/mol. Finally, details on the molecular structures at intermediate and transition states as well as charges in different configurations are discussed.},
doi = {10.1021/acs.jpca.2c02124},
url = {https://www.osti.gov/biblio/1884635},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {ISSN 1089-5639},
number = {31},
volume = {126},
place = {United States},
publisher = {American Chemical Society},
year = {2022},
month = {08}}
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); US Air Force Office of Scientific Research (AFOSR)
Grant/Contract Number:
AC52-07NA27344
OSTI ID:
1884635
Report Number(s):
LLNL-JRNL-830303; 1046068
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 31 Vol. 126; ISSN 1089-5639