{
  "abstract": "p-Block elements are emerging as sustainable alternatives to transition metals in catalysis, but the development of new species capable of redox cycling poses a central challenge to achieving metallomimetic reactivity. Redox-neutral processes offer a powerful strategy to circumvent challenging reductive elimination steps. Despite promising early applications of germanium(II)–ligand cooperativity for stoichiometric bond activation, the use of germylenes in redox-neutral catalysis remains largely limited to hydrofunctionalization of polar unsaturated bonds. Herein, we report the synthesis, reactivity, and catalytic application of a welldefined pyridine dipyrrolide germanium(II) complex, ( tBu PDP)Ge . Stoichiometric studies reveal that ( tBu PDP)Ge activates substrates of varying polarity, including water, N-methylaniline, ammonia-borane, and phenylsilane via a Ge–N cooperative redox-neutral mechanism that bypasses high-energy redox cycling pathways. This germylene serves as a precatalyst for the hydrodefluorination of perfluoro(hetero)arenes. Mechanistic investigations, supported by experimental and computational data, establish a redox-neutral catalytic cycle. Isolation of a well-defined germylene hydride and other key intermediates enabled development of a milder, more efficient catalytic protocol by avoiding a sluggish precatalyst activation step.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "Princeton University"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 7,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Isabelle Fejes"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Alessio Regni"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Yumeng Liao"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Charles J. Ambach"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Javier M. Hurst"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Aleksandr Knyazev"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Jose B. Roque",
      "orcid": "0000-0002-5449-1584"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2yt12yerzhagc.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008387/v1",
  "fulltext_url": null,
  "id": "2yt12yerzhagc",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008387/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",
      "1604|Synthesis and characterization of novel inorganic/organometallic compounds"
    ]
  ],
  "openalex": "W7211867203",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008387/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-07",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/2yt12yerzhagc.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008387",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008387/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1604|Synthesis and characterization of novel inorganic/organometallic compounds",
      "subfield": "inorganic"
    }
  ],
  "title": "Ge–N Cooperativity and Catalytic Hydrodefluorination by a Pyridine Dipyrrolide Germanium Platform",
  "title_text": "Ge–N Cooperativity and Catalytic Hydrodefluorination by a Pyridine Dipyrrolide Germanium Platform",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/2yt12yerzhagc",
  "venue": "ChemRxiv",
  "versions": []
}