{
  "abstract": "Polyphosphazenes are a unique class of polymers, notable for their versatile functionalization and distinctive properties arising from their alternating phosphorus–nitrogen backbone. However, the synthesis of their primary precursor, poly(dichlorophosphazene) ([NPCl2] n ), is notoriously delicate and poorly understood, limiting broader adoption. Herein, we reinvestigate the controlled polymerization of Me3Si─N═PCl3 using quantum mechanical calculations to elucidate its underlying mechanism. Guided by these insights, we optimized the experimental conditions and achieved significantly higher molecular weights than previously reported for this polymerization route. Polymerization occurs at ambient temperature only upon addition of a cationic initiator, such as Ph3PCl2, yielding [NPCl2] n chains of varying lengths. Experiments and DFT calculations indicate that initiation proceeds via three key steps: (i) dissociation of Ph3PCl2 into [Ph3PCl]+ and Cl− ions, dependent on the reaction medium; (ii) nucleophilic attack of Cl− on Me3Si─N═PCl3, producing [N═PCl3]− and eliminating Me3SiCl; (iii) reaction of [N═PCl3]− with [Ph3PCl]+ to form Ph3P─NPCl4, which dissociates to generate additional reactive species, propagating chain growth. The elimination of Me3SiCl, concurrent with [N═PCl3]− formation, constitutes the rate‐limiting step. Accordingly, this type of polymerization can be described as a chloride‐catalyzed cationic process. These findings provide a detailed mechanistic understanding of poly(dichlorophosphazene) formation and offer a basis for optimizing reaction conditions to achieve controlled polymerization.",
  "abstract_shown": true,
  "affiliations": [
    "Institute of Chemistry University of Rostock Rostock Germany",
    "Institute of Polymer Chemistry Johannes Kepler University Linz Austria",
    "Institute For Biomedical Engineering University Medical Center Rostock Rostock Germany",
    "Leibniz‐Institute For Catalysis e.V. Rostock Germany"
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Cornelius Knuth"
    },
    {
      "affs": [
        1
      ],
      "name": "Paul Strasser"
    },
    {
      "affs": [
        0
      ],
      "name": "Carmen Hoth"
    },
    {
      "affs": [
        0
      ],
      "name": "Joerg Harloff"
    },
    {
      "affs": [
        2
      ],
      "name": "Thomas Eickner"
    },
    {
      "affs": [
        1
      ],
      "name": "Ian Teasdale",
      "orcid": "0000-0001-5953-9084"
    },
    {
      "affs": [
        0,
        3
      ],
      "name": "Axel Schulz",
      "orcid": "0000-0001-9060-7065"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/58vtcz5a5ff78.bib",
  "cited_by": 0,
  "doi": "10.1002/chem.71399",
  "fulltext_url": "https://pmc.ncbi.nlm.nih.gov/articles/PMC13716006/",
  "id": "58vtcz5a5ff78",
  "issns": [
    "0947-6539",
    "1521-3765"
  ],
  "landing_url": "https://doi.org/10.1002/chem.71399",
  "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",
      "1605|Advanced Polymer Synthesis and Characterization"
    ]
  ],
  "openalex": "W7172049403",
  "pdf_url": "https://onlinelibrary.wiley.com/doi/pdfdirect/10.1002/chem.71399",
  "pmcid": "PMC13716006",
  "pmid": "42535645",
  "published": "2026-07-31",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/58vtcz5a5ff78.ris",
  "sources": [
    {
      "first_seen": "2026-11-01T12:23:10Z",
      "native_id": "PMC13716006",
      "source": "pmc",
      "url": "https://doi.org/10.1002/chem.71399"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Advanced Polymer Synthesis and Characterization",
      "subfield": "organic"
    }
  ],
  "title": "New Insights into Poly(Dichlorophosphazene) Synthesis via Me3Si─N═PCl3 Polymerization: An Experimental and Theoretical Study",
  "title_text": "New Insights into Poly(Dichlorophosphazene) Synthesis via Me3Si─N═PCl3 Polymerization: An Experimental and Theoretical Study",
  "type": "peer-reviewed",
  "updated_at": "2026-11-01T12:23:10Z",
  "url": "https://research.draconitic.com/paper/58vtcz5a5ff78",
  "venue": "Chemistry (Weinheim an Der Bergstrasse, Germany)",
  "versions": []
}