{
  "abstract": "Dinitrosyl iron complexes (DNICs) are widespread biological nitric oxide (NO) storage and delivery motifs, yet their highly delocalized electronic structure generally resists NO-centered reductive chemistry. Here, we establish ligandcentered reduction as a strategy for unlocking nitroxyl (HNO)-generating DNIC reactivity. A redox-active formazanate ligand (L) stabilizes a super-reduced formal {LFe(NO) 2 } 11 state beyond the conventional {Fe(NO) 2 } 9/10 redox pair. EPR and Mössbauer spectroscopy, together with density functional theory calculations, identify predominantly ligand-centered reduction, yielding an {Fe(NO) 2 } 10 unit coupled to a formazanate radical dianion, L 2−• . Electronic communication between the reduced ligand and the [Fe(NO) 2 ] unit enhances Fe-to-NO π backbonding, consistent with experimental ν(NO) redshifts. Importantly, protonation triggers HNO release, representing an unprecedented example of HNO generation from the super reduced DNIC scaffold. Isotopically distinct H 14 NO/H 15 NO is trapped with PPh 3 , along with the 14/15 N 2 O characterization. Calculations support direct nitrosyl protonation to form an Fe-bound HNO intermediate, followed by solvent-assisted HNO release and subsequent N 2 O formation. These findings establish that ligand-centered electron accommodation coupled to nitrosyl protonation enables HNO generation from a formally super-reduced DNIC, extending DNIC reactivity beyond conventional NO donation.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "Southern Methodist University",
    "University of Alabama",
    "Texas A&M University",
    "Georgetown University",
    "Department of Biochemistry and Biophysics"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 11,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Esther Mosebolatan"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Aruzhan Abdikaiym"
    },
    {
      "affs": [
        0,
        3
      ],
      "name": "Chandradeep Ghosh"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Anagha Kuruvayil"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Saikat Mishra"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Krish Pudu"
    },
    {
      "affs": [
        0,
        4
      ],
      "name": "Jeffery A. Bertke"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Marek Freindorf"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Brad S. Pierce"
    },
    {
      "affs": [
        0,
        3,
        5
      ],
      "name": "Paul A. Lindahl"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Pokhraj Ghosh",
      "orcid": "0000-0002-9306-3144"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/e637f0sqa9031.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15011062/v1",
  "fulltext_url": null,
  "id": "e637f0sqa9031",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011062/v1",
  "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": "W7223672169",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-26",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/e637f0sqa9031.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15011062",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011062/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Metal-Catalyzed Oxygenation Mechanisms",
      "subfield": "inorganic"
    }
  ],
  "title": "Redox-active ligand facilitates HNO generation in a super-reduced dinitrosyl iron complex",
  "title_text": "Redox-active ligand facilitates HNO generation in a super-reduced dinitrosyl iron complex",
  "type": "preprint",
  "updated_at": "2026-11-04T00:20:58Z",
  "url": "https://research.draconitic.com/paper/e637f0sqa9031",
  "venue": "ChemRxiv",
  "versions": []
}