{
  "abstract": "Herein, we investigate the β-thio-δ-diimine (BTDDI) ligand, recently reported as a sulfur containing analogue of the established BODDI framework, as a platform for mono- and bimetallic Cu(I) and Zn(II) chemistry. Sequential metalation enables selective access to homo- and heterobimetallic complexes, including the first structurally characterised Cu/Zn derivative of this ligand class. Replacement of the central oxygen donor by sulfur expands the dinuclear framework, resulting in significantly increased metal–metal separations. The reactivity of these complexes towards CO 2 is strongly dependent on both metal identity and nuclearity: monometallic Cu(I) and Zn(II) complexes and the homobimetallic Cu(I) analogue are unreactive, whereas the Cu/Zn and di-Zn complexes undergo CO 2 activation. The di-Zn complex undergoes selective C–C bond formation at the γ-position of the ligand backbone to give a reversibly formed carboxylate-containing product featuring an unusual tripodal [N,S,O] donor motif. Isotopic labelling, spectroscopic and structural studies establish incorporation of CO 2 into the ligand framework, while DFT calculations reveal substantially lower barriers to γ-C insertion for the bimetallic complexes and identify Zn(II) as a key contributor to stabilisation of the resulting carboxylate through Zn–O interactions and subsequent dimerisation. These results establish a mode of CO 2 activation in which ligand-centred reactivity is coupled to metal-centred substrate stabilisation, with metal identity and nuclearity determining the outcome of the reaction.",
  "abstract_shown": true,
  "affiliations": [
    "School of Chemical, Environmental and Earth Sciences, University of Leicester, University Road, Leicester, UK, LE1 7RH",
    "School of Chemistry",
    "Trinity College Dublin, The University of Dublin"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 5,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Jamie Allen",
      "orcid": "0009-0001-5723-3919"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Diney S. Shanfrezan",
      "orcid": "0009-0002-1749-0985"
    },
    {
      "affs": [
        0
      ],
      "name": "Grace E. Linford-Wood"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Tobias Krämer",
      "orcid": "0000-0001-5842-9553"
    },
    {
      "affs": [
        0
      ],
      "name": "Alexander F. R. Kilpatrick",
      "orcid": "0000-0002-2108-2709"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/0dxv75vqqzvnj.bib",
  "cited_by": 1,
  "doi": "10.26434/chemrxiv.15009332/v1",
  "fulltext_url": null,
  "id": "0dxv75vqqzvnj",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009332/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": "W7214072526",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009332/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-23",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/0dxv75vqqzvnj.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009332",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009332/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:1605|Organometallic Complex Synthesis and Catalysis",
      "subfield": "organic"
    }
  ],
  "title": "A Dinucleating β-Thio-δ-Diiminate Ligand Enables Metal-Dependent CO2 Reactivity in Homo- and Heterobimetallic Zn and Cu Complexes",
  "title_text": "A Dinucleating β-Thio-δ-Diiminate Ligand Enables Metal-Dependent CO2 Reactivity in Homo- and Heterobimetallic Zn and Cu Complexes",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/0dxv75vqqzvnj",
  "venue": "ChemRxiv",
  "versions": []
}