{
  "abstract": "Dioxygen is the oxidant of aerobic life, yet most closed-shell molecules are stable in its presence. 1–4 Conventional accounts of dioxygen activation begin with electron transfer to O 2 , typically from a redox-active metal centre or cofactor. 5–9 Here we show that preparing dioxygen to receive that electron is a separate function, discharged by the electrostatic environment alone, and that the two can be tuned independently. At the equilibrium geometry of neutral O 2 the anion that must receive the electron is unbound; 10,11 a Lewis-acidic field removes this obstacle before any charge moves, a stage we term preactivation . Point charges alone split the O 2 π* manifold and bind the anion at the neutral geometry. Reaction-path calculations show that inner-sphere electron transfer from the Zn–C bond, which generates a superoxide/alkyl-radical pair without metal-centred redox chemistry, is rate-determining. Calibrated on dialkylzincs alone, the in-plane anisotropy of the field gradient, with one term in the charge and distance of the metal resolved within the same series, predicts the π* splitting to within 7% in four enzyme active sites containing iron, copper, nickel or no metal. The electrostatic contribution of an enzyme active site to preactivation can thus be quantified on a scale calibrated with redox-silent organozinc compounds.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "name": "Grzegorz Jędrzejczyk",
      "orcid": "0009-0009-3304-0467"
    },
    {
      "name": "Janusz Lewiński",
      "orcid": "0000-0002-3407-0395"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/3xfephye8jjhv.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15007775/v2",
  "fulltext_url": null,
  "id": "3xfephye8jjhv",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007775/v2",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1604|Metal-Catalyzed Oxygenation Mechanisms"
    ]
  ],
  "openalex": "W7221611976",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15007775/v2",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-13",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/3xfephye8jjhv.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15007775",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007775/v3"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Metal-Catalyzed Oxygenation Mechanisms",
      "subfield": "inorganic"
    }
  ],
  "title": "Electrostatic preactivation, a missing step in dioxygen activation",
  "title_text": "Electrostatic preactivation, a missing step in dioxygen activation",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/3xfephye8jjhv",
  "venue": "ChemRxiv",
  "versions": []
}