{
  "abstract": "Herein, we show that a phosphonium-substituted diphosphaindenylide (PPIPh) functions as a genuine two-electron redox-active π-ligand. The cationic manganese complex [Mn(CO)3(η5‑PPIPh)][BArF24] ([1][BArF24]) undergoes a reversible two-electron reduction to afford the isolable anionic complex [K(18c6)][Mn(CO)3(η3‑PPIPh)]·([K(18c6)][BArF24])n (n = 1 – 5). This constitutes the first isolable and structurally characterized two-electron redox couple of an indenyl-derived manganese complex, which has previously eluded isolation with purely carbocyclic indenyl ligands. Computational studies establish manganese in the +I oxidation state in both complexes, demonstrating that the redox process is exclusively ligand-centered. The redox-activity of the ligand also translates into chemical reactivity, with the anionic complex affording 91% yield in the hydroboration of 2-acetonaphthone, compared to only 7% for [1][BArF24].",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "name": "David Zuber"
    },
    {
      "name": "Michael Neuwirt"
    },
    {
      "name": "Peter Coburger",
      "orcid": "0000-0003-1387-4148"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/5em1em69vzwx2.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008539/v1",
  "fulltext_url": null,
  "id": "5em1em69vzwx2",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008539/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",
      "1605|Organometallic Complex Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7212009091",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008539/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-09",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/5em1em69vzwx2.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008539",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008539/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organometallic Complex Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "Unlocking Ligand-Centered Redox Activity in an Indenyl Framework through Phosphorus Substitution",
  "title_text": "Unlocking Ligand-Centered Redox Activity in an Indenyl Framework through Phosphorus Substitution",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/5em1em69vzwx2",
  "venue": "ChemRxiv",
  "versions": []
}