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Context <p>This work delves into inhibition chemistry of CF<sub>3</sub>CF<sub>2</sub>N=CFCF<sub>3</sub> triggered by H radical. Analyses of electrostatic potential on the van der Waals surface reveal that the -N=CF- double bond has two reactive sites for H addition, particularly at the C atom with low-energy antibonding orbitals, and both N and F atoms present strong electron-rich characters, as identified by global and local minima of negative electrostatic potential, respectively. Energetics and kinetics demonstrate that the reactants&#xa0;of CF<sub>3</sub>CF<sub>2</sub>N=CFCF<sub>3</sub> + H prefer to undergo entrance additions rather than abstractions and substitutions. The addition to Mb1 dominates at low temperatures, the addition to Mb2 and the dissociation of Mb1 to Pb12 (CF<sub>3</sub>CF<sub>2</sub>N=CHF + CF<sub>3</sub>) show fierce competition in leading role at moderate temperature zone, and then the dissociation of Mb2 to Pb16 (CF<sub>3</sub>C = NH + C<sub>2</sub>F<sub>5</sub>) controls the overall mechanism at elevated temperatures. These four exothermic reactions release heat, which may enhance combustion, while two β-C–C scissions greatly contribute to inhibition by releasing CF<sub>3</sub> and C<sub>2</sub>F<sub>5</sub> moieties.</p> Method <p>High-level quantum chemical methods and transition-state theory-based kinetic simulations were employed in this study. The electrostatic potential on the van der Waals surface of CF<sub>3</sub>CF<sub>2</sub>N=CFCF<sub>3</sub> was analyzed at the M06-2X/Def-TZVP level. Potential energy surfaces were characterized at the CCSD(T)/6–311+ +G(d,p) level based on B3LYP/6–311+ +G(d,p) optimized geometries. Kinetics and branching ratios for entrance additions and major consumption dissociations were predicted by solving RRKM/master-equations within 300–3000&#xa0;K and 0.01–100&#xa0;atm.</p>

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Kinetic and mechanistic study of H radical capture reaction in inhibition chemistry of CF3CF2N = CFCF3

  • 期刊论文

  • 发表日期：

    2026年4月1日

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  • Huiting Bian,
  • Jiantao Li,
  • Yongjin Wang,
  • Xinran Zhang,
  • Qian Li,
  • Feng Zhu,
  • Yang Wang,
  • Huiling Jiang

摘要

Context

This work delves into inhibition chemistry of CF3CF2N=CFCF3 triggered by H radical. Analyses of electrostatic potential on the van der Waals surface reveal that the -N=CF- double bond has two reactive sites for H addition, particularly at the C atom with low-energy antibonding orbitals, and both N and F atoms present strong electron-rich characters, as identified by global and local minima of negative electrostatic potential, respectively. Energetics and kinetics demonstrate that the reactants of CF3CF2N=CFCF3 + H prefer to undergo entrance additions rather than abstractions and substitutions. The addition to Mb1 dominates at low temperatures, the addition to Mb2 and the dissociation of Mb1 to Pb12 (CF3CF2N=CHF + CF3) show fierce competition in leading role at moderate temperature zone, and then the dissociation of Mb2 to Pb16 (CF3C = NH + C2F5) controls the overall mechanism at elevated temperatures. These four exothermic reactions release heat, which may enhance combustion, while two β-C–C scissions greatly contribute to inhibition by releasing CF3 and C2F5 moieties.

Method

High-level quantum chemical methods and transition-state theory-based kinetic simulations were employed in this study. The electrostatic potential on the van der Waals surface of CF3CF2N=CFCF3 was analyzed at the M06-2X/Def-TZVP level. Potential energy surfaces were characterized at the CCSD(T)/6–311+ +G(d,p) level based on B3LYP/6–311+ +G(d,p) optimized geometries. Kinetics and branching ratios for entrance additions and major consumption dissociations were predicted by solving RRKM/master-equations within 300–3000 K and 0.01–100 atm.