{
  "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.",
  "abstract_shown": true,
  "affiliations": [
    "Yili Normal University , , ,",
    "Harbin Institute of Technology , , ,",
    "Harbin University , , ,"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Hongyi Wang"
    },
    {
      "affs": [
        2
      ],
      "name": "Siwei Zhao"
    },
    {
      "affs": [
        0
      ],
      "name": "Jiabin Zhu"
    },
    {
      "affs": [
        0
      ],
      "name": "Siqi Yang"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Jiaxu Zhang",
      "orcid": "0000-0002-3125-7824"
    },
    {
      "affs": [
        0
      ],
      "name": "Baoshan Hou",
      "orcid": "0009-0008-3421-1267"
    },
    {
      "affs": [
        0
      ],
      "name": "Li Yang",
      "orcid": "0000-0002-0143-3524"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/25cwhsvqx2sea.bib",
  "cited_by": 0,
  "doi": "10.1021/acsomega.6c08972",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13736869/",
  "id": "25cwhsvqx2sea",
  "issns": [
    "2470-1343"
  ],
  "landing_url": "https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c08972/5453308/Abundant-Reaction-Mechanisms-for-the-Nucleophile",
  "language": "en",
  "licence": "CC-BY-NC-ND-4.0",
  "licence_label": "CC BY-NC-ND 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Article"
    ],
    [
      "openalex",
      "1605|Chemical Reaction Mechanisms"
    ]
  ],
  "openalex": "W7222815442",
  "pdf_url": "https://pubs.acs.org/doi/pdf/10.1021/acsomega.6c08972",
  "pmcid": "PMC13736869",
  "pmid": "42991898",
  "published": "2026-10-17",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/25cwhsvqx2sea.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:18:39Z",
      "native_id": "10.1021/acsomega.6c08972",
      "source": "crossref",
      "url": "https://pubs.acs.org/acsodf/article/doi/10.1021/acsomega.6c08972/5453308/Abundant-Reaction-Mechanisms-for-the-Nucleophile"
    },
    {
      "first_seen": "2026-11-09T12:22:14Z",
      "native_id": "PMC13736869",
      "source": "pmc",
      "url": "https://doi.org/10.1021/acsomega.6c08972"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Chemical Reaction Mechanisms",
      "subfield": "organic"
    }
  ],
  "title": "Abundant Reaction Mechanisms for the α-Nucleophile-Involved Reaction of HOO– + CH3Br",
  "title_text": "Abundant Reaction Mechanisms for the α-Nucleophile-Involved Reaction of HOO– + CH3Br",
  "type": "peer-reviewed",
  "updated_at": "2026-11-09T12:22:14Z",
  "url": "https://research.draconitic.com/paper/25cwhsvqx2sea",
  "venue": "ACS Omega",
  "versions": []
}