{
  "abstract": "Carbene functionalization through direct substitution at the carbene center is well established for Fischer-type carbene complexes of early transition metals but remains exceedingly rare for carbene complexes of late transition metals. Here, we report a general strategy for carbene functionalization at coinage metals based on nucleophilic substitution of difluorocarbene complexes. Persistent LnAu(I)=CF2+ complexes undergo efficient fluorine-to-nitrogen and fluorine-to-oxygen substitution with nucleophiles, providing direct access to fluoro-amino- and fluoro-oxy-carbene complexes. The methodology is also applicable to transient Au(I) difluorocarbenes and extends to Cu(I) and Ag(I) systems, enabling carbene functionalization across the coinage metal series. Access to a family of closely related group 11 carbenes (10 examples) enables direct comparison of their structure and bonding. Spectroscopic and computational studies reveal that fluorine-to-nitrogen substitution profoundly impacts the electronic structure of the carbene complex, affording species best described as metalated fluoro-iminium ions. Density functional theory supports a highly exergonic addition−elimination mechanism driven by Si−F bond formation and identifies metal-to-carbene π-backdonation as the key factor governing the stability of difluorocarbene intermediates, following the trend Au > Cu > Ag. These findings establish nucleophilic substitution as a general strategy for the functionalization of coinage-metal carbene complexes and demonstrate that heteroatom substitution provides direct access to electronically distinct metalated iminium and oxonium species.",
  "abstract_shown": true,
  "affiliations": [
    "Université de Toulouse, CNRS , , UMR 5069, 118 Route de Narbonne , Cedex 09,",
    "Université de Pau et des Pays de l’Adour, CNRS , , UMR 5254, Hélioparc, 2 Avenue du Président Angot, Cedex 09 , ,",
    "Université de Toulouse, CNRS , , UAR 2599), 118 Route de Narbonne , Cedex 09,"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "David Vesseur",
      "orcid": "0009-0005-3719-574X"
    },
    {
      "affs": [
        0
      ],
      "name": "Shuo Li"
    },
    {
      "affs": [
        0
      ],
      "name": "Juan Carlos Pérez-Sánchez",
      "orcid": "0000-0002-5298-8351"
    },
    {
      "affs": [
        1
      ],
      "name": "Nina Albouy"
    },
    {
      "affs": [
        2
      ],
      "name": "Sonia Mallet-Ladeira"
    },
    {
      "affs": [
        1
      ],
      "name": "Karinne Miqueu",
      "orcid": "0000-0002-5960-1877"
    },
    {
      "affs": [
        0
      ],
      "name": "Didier Bourissou",
      "orcid": "0000-0002-0249-1769"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/cn8zhjbhz1558.bib",
  "cited_by": 0,
  "doi": "10.1021/jacsau.6c00964",
  "fulltext_url": null,
  "id": "cn8zhjbhz1558",
  "issns": [
    "2691-3704"
  ],
  "landing_url": "https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c00964/5465164/Nucleophilic-Substitution-at-Difluoro-Carbene",
  "language": null,
  "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": [],
  "openalex": null,
  "pdf_url": "https://pubs.acs.org/doi/pdf/10.1021/jacsau.6c00964",
  "pmcid": null,
  "pmid": null,
  "published": "2026-11-05",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/cn8zhjbhz1558.ris",
  "sources": [
    {
      "first_seen": "2026-11-06T00:21:08Z",
      "native_id": "10.1021/jacsau.6c00964",
      "source": "crossref",
      "url": "https://pubs.acs.org/jaaucr/article/doi/10.1021/jacsau.6c00964/5465164/Nucleophilic-Substitution-at-Difluoro-Carbene"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "issn:2691-3704",
      "subfield": "general"
    }
  ],
  "title": "Nucleophilic Substitution at Difluoro-Carbene Complexes of the Coinage Metals",
  "title_text": "Nucleophilic Substitution at Difluoro-Carbene Complexes of the Coinage Metals",
  "type": "peer-reviewed",
  "updated_at": "2026-11-07T00:21:06Z",
  "url": "https://research.draconitic.com/paper/cn8zhjbhz1558",
  "venue": "JACS Au",
  "versions": [
    {
      "doi": "10.26434/chemrxiv.15004939/v1",
      "pid": null,
      "relation": "preprint",
      "title": null,
      "venue": null
    }
  ]
}