Abundant Reaction Mechanisms for the α-Nucleophile-Involved Reaction of HOO– + CH3Br
- 1Yili Normal University , , ,
- 2Harbin Institute of Technology , , ,
- 3Harbin University , , ,
Abstract
The reaction of the peroxide ion with CH3Br was investigated by direct dynamics simulation. A variety of reaction mechanisms, i.e., front-side complex, proton exchange, and H-migration mechanisms, were found, and the nature of these mechanisms was discussed in detail, which is essential for the dynamical behavior of diatomic or triatomic nucleophilic substitution reactions involving an α-nucleophile. Furthermore, the dynamic characteristics of X– + CH3Y reactions (X= HOO and OH; Y = Cl, Br, and I) were compared to reveal the influences of the nucleophile and leaving group on the α-nucleophile reactions. Atomistic reaction mechanism analyses find that HOO– + CH3Br collisions show similar reaction probabilities to the HO– + CH3Br reaction, although the proton affinity of HO– is larger than that of HOO–, which reveals the enhanced reactivity of HOO– and the presence of an α-effect relative to the normal nucleophiles. For the HOO– + CH3Br reaction, the indirect mechanisms are dominant at low collision energy, and a dramatic transition from complex-mediated indirect to direct occurs when changing HOO– to the normal nucleophile HO–. Besides, with the leaving group ability trend of Cl < Br, the branching ratio of the direct mechanism increases from 7 to 17%, and simultaneously, the ratio of the indirect mechanism decreases, which is attributed to the lower central barrier and an “earlier” transition state for the HOO– + CH3Br reaction.
Related
- Highly twinned cobalt selenide with abundant selenium vacancies for efficient nitrogen reduction reaction
- Understanding oxygen reduction/evolution reaction and degradation mechanisms on BaCo0.4Fe0.4Zr0.1Y0.1O3-δ electrode in protonic ceramic electrochemical cells via the distribution of relaxation times analysis
- TSBench: A physics-grounded benchmark for evaluating LLM understanding of chemical reaction mechanisms
- Recent Progress in NiFe-LDH Electrocatalysts: Synthesis, Mechanisms, and Performance in the Oxygen Evolution Reaction
- Nickel-based layered double hydroxide oxygen evolution electrocatalysts: From reaction mechanisms to design strategies and material modification
BibTeX
@article{wang2026abundant,
title = {{Abundant Reaction Mechanisms for the α-Nucleophile-Involved Reaction of HOO– + CH3Br}},
author = {Hongyi Wang and Siwei Zhao and Jiabin Zhu and Siqi Yang and Jiaxu Zhang and Baoshan Hou and Li Yang},
journal = {ACS Omega},
year = {2026},
month = oct,
doi = {10.1021/acsomega.6c08972},
url = {https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c08972/5453308/Abundant-Reaction-Mechanisms-for-the-Nucleophile},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Abundant Reaction Mechanisms for the α-Nucleophile-Involved Reaction of HOO– + CH3Br
AU - Hongyi Wang
AU - Siwei Zhao
AU - Jiabin Zhu
AU - Siqi Yang
AU - Jiaxu Zhang
AU - Baoshan Hou
AU - Li Yang
PY - 2026
DA - 2026/10/17
JO - ACS Omega
DO - 10.1021/acsomega.6c08972
UR - https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c08972/5453308/Abundant-Reaction-Mechanisms-for-the-Nucleophile
AB - The reaction of the peroxide ion with CH3Br was investigated by direct dynamics simulation. A variety of reaction mechanisms, i.e., front-side complex, proton exchange, and H-migration mechanisms, were found, and the nature of these mechanisms was discussed in detail, which is essential for the dynamical behavior of diatomic or triatomic nucleophilic substitution reactions involving an α-nucleophile. Furthermore, the dynamic characteristics of X– + CH3Y reactions (X= HOO and OH; Y = Cl, Br, and I) were compared to reveal the influences of the nucleophile and leaving group on the α-nucleophile reactions. Atomistic reaction mechanism analyses find that HOO– + CH3Br collisions show similar reaction probabilities to the HO– + CH3Br reaction, although the proton affinity of HO– is larger than that of HOO–, which reveals the enhanced reactivity of HOO– and the presence of an α-effect relative to the normal nucleophiles. For the HOO– + CH3Br reaction, the indirect mechanisms are dominant at low collision energy, and a dramatic transition from complex-mediated indirect to direct occurs when changing HOO– to the normal nucleophile HO–. Besides, with the leaving group ability trend of Cl < Br, the branching ratio of the direct mechanism increases from 7 to 17%, and simultaneously, the ratio of the indirect mechanism decreases, which is attributed to the lower central barrier and an “earlier” transition state for the HOO– + CH3Br reaction.
SN - 2470-1343
ER -