{
  "abstract": "Discovery and optimization of cross-coupling catalysts require catalyst activation strategies that balance the operational simplicity of air-stable precatalysts with the need for air-sensitive, lowcoordinate and -valent intermediates for substrate activation and turnover. Here we introduce a general approach for on-demand catalyst activation via two-electron photoreduction of air-stable phosphine-ligated palladium(II) oxalates. The platform exploits rapid ligand exchange at (MeCN)2Pd(ox) to enable modular assembly of catalyst photoprecursors from a single precursor. In crystallo photochemistry and single-crystal Raman spectroscopy of phosphine-supported Pd oxalates establish that photoactivation proceeds via the extrusion of two molecules of CO2 and provide the Uirst crystallographic characterization of a Pd–CO2 adduct. Two-electron photoactivation translates to the solution phase to provide a platform to access Pd oxidative addition complexes (OACs) and to generate poison-free, on-cycle catalyst intermediates. The combination of rapid and quantitative ligand exchange coupled with facile two-electron photoreduction enables application in highthroughput experimentation (HTE) workUlows and on-plate ligand screening. Photogenerated catalysts are competitive with state-of-the-art precatalysts in both C–N cross-coupling and a newly developed base-free Suzuki reaction. These results establish Pd oxalates as general, photoactivated precursors to unsaturated catalyst intermediates that unlock streamlined, combinatorial workUlows for catalyst discovery and data-driven optimization.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "Texas A&M University",
    "University of Pennsylvania",
    "Argonne National Laboratory",
    "University of Chicago",
    "Center for Nanoscale Materials"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 10,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Aishanee Sur"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Pritam Roychowdhury"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Subham Sarkar"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Matthew T. Figgins"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Saim Waheed"
    },
    {
      "affs": [
        3,
        4
      ],
      "name": "Yu-Sheng Chen"
    },
    {
      "affs": [
        5,
        3
      ],
      "name": "David J. Gosztola"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Nattamai Bhuvanesh"
    },
    {
      "affs": [
        0,
        2
      ],
      "name": "Andrew F. Zahrt"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "David C. Powers",
      "orcid": "0000-0003-3717-2001"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/b3n7z742r59vy.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010046/v1",
  "fulltext_url": null,
  "id": "b3n7z742r59vy",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010046/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|Catalytic Cross-Coupling Reactions"
    ]
  ],
  "openalex": "W7220848243",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-07",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/b3n7z742r59vy.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:22Z",
      "native_id": "10.26434/chemrxiv.15010046",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010046/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Catalytic Cross-Coupling Reactions",
      "subfield": "organic"
    }
  ],
  "title": "Two-Electron Photoreduction of Pd(II) Oxalates: In Crystallo Synthesis and Catalysis",
  "title_text": "Two-Electron Photoreduction of Pd(II) Oxalates: In Crystallo Synthesis and Catalysis",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:22Z",
  "url": "https://research.draconitic.com/paper/b3n7z742r59vy",
  "venue": "ChemRxiv",
  "versions": []
}