{
  "abstract": "We report a method for converting white phosphorus (P4) directly into tetra‐ and pentaphosphanes using N‐heterocyclic carbene (NHC) copper(I) complexes. The insertion of P4 into the metal‐element bonds of the NHC complexes (6Dipp)Cu(Nu) [Nu = OtBu and N(iPr)2] affords [(6Dipp)Cu(κ 2‐P4OtBu)] (1) and [(6Dipp)Cu{κ 2‐P4N(iPr)2}] (3), which exhibit rotation of the [P4Nu]− ligand around the copper center in solution. This fluxional process is suppressed at low temperature, as shown by variable‐temperature 31P{1H} NMR spectroscopy. Treatment of 1 with W(CO)5(thf) resulted in the formation of the bimetallic complex [(6Dipp)Cu(μ,κ 2:κ 1‐P4OtBu){W(CO)5}] (2) which does not show fluxional behavior. Reactions of 1 and 3 with p‐block element halides release metal‐free asymmetrically substituted bicyclo[1.1.0]tetraphosphabutane ‘butterfly’ compounds. The polyphosphanes P4(PMes2)(OtBu) (4a), P4[P{N(iPr)2}2](OtBu) (4b), P4[P{N(iPr)2}2]{N(iPr)2} (4c), and P4(BPh2){N(iPr)2} (5) were isolated as stable compounds. Treatment of 4c with the NHC IMes induces further phosphorus–phosphorus bond cleavage and rearrangement to give NHC‐phosphinidene adduct [cyclo‐P3{N(iPr)2}(P{N(iPr)2}2)(P═IMes)] (6). Compound 4c also reacts with W(CO)5(thf) and CuBr·SMe2 to give coordination complexes [W(CO)5{κ 1‐P4(P{N(iPr)2}2)(N{iPr}2)}] (7) and [Cu(Br){κ 2‐P4(P{N(iPr)2}2)(N{iPr}2)}] (8), respectively, demonstrating the ability of 4c to serve as a mono‐ and bidentate ligand for transition metals. All compounds were characterized crystallographically and spectroscopically.",
  "abstract_shown": true,
  "affiliations": [
    "Institute of Inorganic Chemistry University of Regensburg Regensburg Germany"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 5,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Thomas M. Horsley Downie",
      "orcid": "0000-0001-5027-450X"
    },
    {
      "affs": [
        0
      ],
      "name": "Sophia A. Vogler",
      "orcid": "0009-0007-3106-2836"
    },
    {
      "affs": [
        0
      ],
      "name": "Gábor Balázs",
      "orcid": "0000-0003-3497-7082"
    },
    {
      "affs": [
        0
      ],
      "name": "Francesco Cirigliano"
    },
    {
      "affs": [
        0
      ],
      "name": "Robert Wolf",
      "orcid": "0000-0003-4066-6483"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/8c0tprng5gsp0.bib",
  "cited_by": 0,
  "doi": "10.1002/anie.8252739",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13725586/",
  "id": "8c0tprng5gsp0",
  "issns": [
    "1433-7851",
    "1521-3773"
  ],
  "landing_url": "https://doi.org/10.1002/anie.8252739",
  "language": "en",
  "licence": "CC-BY-4.0",
  "licence_label": "CC BY 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Research Article"
    ],
    [
      "openalex",
      "1604|Synthesis and characterization of novel inorganic/organometallic compounds"
    ]
  ],
  "openalex": "W7213543993",
  "pdf_url": "https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/anie.8252739",
  "pmcid": "PMC13725586",
  "pmid": "42757981",
  "published": "2026-09-18",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/8c0tprng5gsp0.ris",
  "sources": [
    {
      "first_seen": "2026-11-04T12:23:56Z",
      "native_id": "PMC13725586",
      "source": "pmc",
      "url": "https://doi.org/10.1002/anie.8252739"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Synthesis and characterization of novel inorganic/organometallic compounds",
      "subfield": "inorganic"
    }
  ],
  "title": "NHC‐Copper(I)‐Mediated Functionalization of White Phosphorus",
  "title_text": "NHC‐Copper(I)‐Mediated Functionalization of White Phosphorus",
  "type": "peer-reviewed",
  "updated_at": "2026-11-06T12:21:47Z",
  "url": "https://research.draconitic.com/paper/8c0tprng5gsp0",
  "venue": "Angewandte Chemie (International Ed. in English)",
  "versions": []
}