{
  "abstract": "The activation and reduction of molecular oxygen at transition metal centers are central to both enzymatic catalysis and energy conversion. Here, we report the first direct observation of a hydrogen-bonding-assisted, quasi-reversible superoxo (Fe III ─O 2 ˙ˉ)/peroxo (Fe III ─O 2 2 ˉ) redox couple in a heme model complex using conventional cyclic voltammetry. Urea groups installed in the second coordination sphere (SCS) of an iron-porphyrin (ααUrFe) form a hydrogen-bonding network that stabilizes the Fe III ─O 2 ˙ˉintermediate through interaction with a trapped water molecule. Spectroscopic studies and DFT calculations reveal that one-electron reduction of the low-spin end-on Fe III ─O 2 ˙ˉspecies generates a low-spin end-on Fe III ─O 2 2 ˉadduct with minimal structural reorganization. These findings provide the first synthetic demonstration of a biologically relevant end-on peroxo species stabilized by hydrogen-bonding \"pull effect\" in the SCS and highlight the critical role of second-sphere interactions in modulating O 2 activation pathways in bioinspired catalysts.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "name": "Adelais Trapali"
    },
    {
      "name": "Régis Guillot"
    },
    {
      "name": "Christian Herrero"
    },
    {
      "name": "Sylvain Bertaina"
    },
    {
      "name": "Athanassios Coutsolelos"
    },
    {
      "name": "Maylis Orio"
    },
    {
      "name": "Zakaria Halime"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2hxdq60zn003x.bib",
  "cited_by": 0,
  "doi": "10.1002/chem.71748",
  "fulltext_url": null,
  "id": "2hxdq60zn003x",
  "issns": [
    "0947-6539",
    "1521-3765"
  ],
  "landing_url": "https://hal.science/hal-05768819v1",
  "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": [
    [
      "hal",
      "0.chim"
    ],
    [
      "openalex",
      "1604|Metal-Catalyzed Oxygenation Mechanisms"
    ]
  ],
  "openalex": "W7214801765",
  "pdf_url": "https://hal.science/hal-05768819/document",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-29",
  "publisher": "Wiley-VCH Verlag",
  "ris": "https://research.draconitic.com/paper/2hxdq60zn003x.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:43Z",
      "native_id": "hal-05768819",
      "source": "hal",
      "url": "https://hal.science/hal-05768819v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Metal-Catalyzed Oxygenation Mechanisms",
      "subfield": "inorganic"
    }
  ],
  "title": "Direct Observation of a Hydrogen‐Bonding Assisted Quasi‐Reversible Superoxo/Peroxo Interconversion in a Heme Model",
  "title_text": "Direct Observation of a Hydrogen‐Bonding Assisted Quasi‐Reversible Superoxo/Peroxo Interconversion in a Heme Model",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:17:43Z",
  "url": "https://research.draconitic.com/paper/2hxdq60zn003x",
  "venue": "Chemistry - A European Journal",
  "versions": []
}