{
  "abstract": "Low-valent tin hydrides display hydride donor properties that differ markedly from those of conventional organotin(IV) hydrides, yet their catalytic applications have remained largely confined to reactions of polar multiple bonds. Herein, we exploit this distinct reactivity for catalytic C–F bond activation and investigate the mechanism underlying the hydrodefluorination of polyfluoroarenes. An isolable diketiminate-supported Sn(II) fluoride efficiently catalyses the reaction using phenylsilane as terminal hydride source. Stoichiometric and spectroscopic studies establish rapid fluoride–hydride exchange between the stannylene fluoride and phenylsilane, generating a catalytically competent stannylene hydride that directly reacts with polyfluoroarenes to form the hydrodefluorination product and regenerate the Sn(II) fluoride. Density functional theory calculations of its hydricity reveals a substantially greater thermodynamic propensity for hydride transfer than n Bu 3 SnH and further distinguish between two plausible pathways for C–F activation: direct hydride transfer proceeds through concerted nucleophilic aromatic substitution ( c S N Ar) and is favoured over competing oxidative addition to Sn(II). The resulting catalytic cycle therefore operates entirely at Sn(II), combining fluoride–hydride exchange with polar C–F substitution rather than Sn(II)/Sn(IV) redox cycling. These findings establish low-valent tin hydrides as competent intermediates for catalytic C–F bond activation and illustrate how their pronounced hydride donor ability can extend the mechanistic toolbox of stannylene catalysis.",
  "abstract_shown": true,
  "affiliations": [
    "Organisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, Heidelberg, Baden-Württemberg, Germany, 69120"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Iris Ballmaier",
      "orcid": "0009-0005-9836-2193"
    },
    {
      "affs": [
        0
      ],
      "name": "Destiny L. T. Brumm"
    },
    {
      "affs": [
        0
      ],
      "name": "Tobias Morack",
      "orcid": "0000-0003-2045-730X"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/9yd464v7x89dv.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008300/v1",
  "fulltext_url": null,
  "id": "9yd464v7x89dv",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008300/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",
      "3003|Fluorine in Organic Chemistry"
    ]
  ],
  "openalex": "W7208764944",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008300/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-04",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/9yd464v7x89dv.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008300",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008300/v1"
    }
  ],
  "subjects": [
    {
      "field": "medicine",
      "origin": "openalex:3003|Fluorine in Organic Chemistry",
      "subfield": "pharmacology-toxicology"
    }
  ],
  "title": "Stannylene hydrides as key intermediates in redox neutral Sn(II)/Sn(II) catalysis: Hydrodefluorination as a case study",
  "title_text": "Stannylene hydrides as key intermediates in redox neutral Sn(II)/Sn(II) catalysis: Hydrodefluorination as a case study",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/9yd464v7x89dv",
  "venue": "ChemRxiv",
  "versions": []
}