{
  "abstract": "When THF solutions of cage-like trans-Fe(CO) 3 (P((CH 2 ) n ) 3 P) ( 1 , n = a /10, b /12, c /14, d /16, e /18) are exposed to a potassium mirror, reduction occurs to give ferrate salts of the formula 2K + [(R 3 P)(CO) 3 Fe] 2– , as supported by IR data. Following additions of excess CO and methanol, the dibridgehead diphosphines P((CH 2 ) n ) 3 P ( 1a-e ) are isolated as white solids in 61-98% yields (average 80%) as mixtures of in/in and out/out isomers that interconvert by homeomorphic isomerization. This protocol represents an alternative to a photochemical demetalation that requires PMe 3 , as well as oxidative recipes that give dibridgehead diphosphine dioxides 1a-e ·2O with byproducts that are difficult to remove. The practicality of the new route is demonstrated by a half gram-scale synthesis of 1b .",
  "abstract_shown": true,
  "affiliations": [
    "Chemistry, Texas A&M University, Department of Chemistry, Texas A&M University, College Station, Texas, United States, 77842-3012"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 2,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Simon M. Popovic"
    },
    {
      "affs": [
        0
      ],
      "name": "John A. Gladysz"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/fztjpv3mj3qjs.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010058/v1",
  "fulltext_url": null,
  "id": "fztjpv3mj3qjs",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010058/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "1605|Organometallic Complex Synthesis and Catalysis"
    ]
  ],
  "openalex": "W7220970710",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15010058/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-07",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/fztjpv3mj3qjs.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010058",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010058/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organometallic Complex Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "A New Route to Macrobicyclic Dibridgehead Diphopsphines P((CH ₂ ) n ) ₃ P; Reductive Demetalation of Cage-Like Fe(CO) ₃ Adducts",
  "title_text": "A New Route to Macrobicyclic Dibridgehead Diphopsphines P((CH ₂ ) n ) ₃ P; Reductive Demetalation of Cage-Like Fe(CO) ₃ Adducts",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/fztjpv3mj3qjs",
  "venue": "ChemRxiv",
  "versions": []
}