{
  "abstract": "Understanding how ligand architecture and conformational flexibility govern reactivity and selectivity in dinuclear metal complexes is essential for the rational design of catalysts. Macrocyclic ligands provide a unique platform to control metalmetal distance as well as the geometry of reactive intermediates; however the relative importance of these factors remains unclear. Herein, we report a series of dinuclear zinc complexes supported by bis(imino)diphenylamido macrocyclic ligands with tunable ring sizes, which exhibit divergent selectivity in CO 2 -to-isocyanate transformations. Varying the linker length between the binding pockets dictates the conformation of key siloxide intermediates, and thus their ability to react further with CO 2 , leading to either isocyanate or silyl ether products. These results establish liganddriven conformational control as a key design principle governing reactivity in dinuclear metal complexes, beyond simple metalmetal distance considerations.",
  "abstract_shown": true,
  "affiliations": [
    "Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, Utrecht, Netherlands, 3584 CG",
    "Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, PO Box 56, Dunedin, New Zealand, 9054",
    "Faculty of Science, Utrecht University, Universiteitsweg 99, Utrecht, Netherlands, 3584 CG",
    "Department of Chemistry, Imperial College London, MRSH, London , London, United Kingdom"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Timo Q. Hokke"
    },
    {
      "affs": [
        0
      ],
      "name": "Lars Killian"
    },
    {
      "affs": [
        0
      ],
      "name": "Dylan van Tongeren"
    },
    {
      "affs": [
        1
      ],
      "name": "Michael S. Bennington"
    },
    {
      "affs": [
        2
      ],
      "name": "Martin Lutz"
    },
    {
      "affs": [
        1
      ],
      "name": "Sally Brooker"
    },
    {
      "affs": [
        3
      ],
      "name": "Charles Romain"
    },
    {
      "affs": [
        0
      ],
      "name": "Arnaud Thevenon",
      "orcid": "0000-0002-5543-6595"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/8gj11s2nh723z.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009526/v1",
  "fulltext_url": null,
  "id": "8gj11s2nh723z",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009526/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",
      "1508|Carbon dioxide utilization in catalysis"
    ]
  ],
  "openalex": "W7214572746",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009526/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-28",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/8gj11s2nh723z.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009526",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009526/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Conformational control for selective CO2-to-isocyanate conversion in a series of dizinc macrocycle complexes",
  "title_text": "Conformational control for selective CO2-to-isocyanate conversion in a series of dizinc macrocycle complexes",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/8gj11s2nh723z",
  "venue": "ChemRxiv",
  "versions": []
}