Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Naphthalene with Acetyl Nitrate in the Gas Phase

Steele, Brad A.; Zhang, Mao-Xi; Kuo, I-Feng W.

doi:10.1021/acs.jpca.2c02124

Single-Step Mechanism for Regioselective Nitration of 9,10-BN-Naphthalene with Acetyl Nitrate in the Gas Phase

Journal Article · Tue Aug 02 00:00:00 EDT 2022 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.2c02124· OSTI ID:1884635

^[1]; Zhang, Mao-Xi ^[1]; Kuo, I-Feng W. ^[1]

Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: US Air Force Office of Scientific Research (AFOSR); USDOE National Nuclear Security Administration (NNSA)

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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