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PreprintCC BY-NC-NDChemRxiv

Conformational control for selective CO2-to-isocyanate conversion in a series of dizinc macrocycle complexes

  • Timo Q. Hokke1
  • Lars Killian1
  • Dylan van Tongeren1
  • Michael S. Bennington2
  • Martin Lutz3
  • Sally Brooker2
  • Charles Romain4
  • Arnaud Thevenon1
4 affiliations
  1. 1Organic Chemistry and Catalysis, Institute for Sustainable and Circular Chemistry, Faculty of Science, Utrecht University, Universiteitsweg 99, Utrecht, Netherlands, 3584 CG
  2. 2Department of Chemistry and the MacDiarmid Institute for Advanced Materials and Nanotechnology, University of Otago, PO Box 56, Dunedin, New Zealand, 9054
  3. 3Faculty of Science, Utrecht University, Universiteitsweg 99, Utrecht, Netherlands, 3584 CG
  4. 4Department of Chemistry, Imperial College London, MRSH, London , London, United Kingdom
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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.

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Cite

BibTeXRIS
BibTeX
@misc{hokke2026conformational,
  title = {{Conformational control for selective CO2-to-isocyanate conversion in a series of dizinc macrocycle complexes}},
  author = {Timo Q. Hokke and Lars Killian and Dylan van Tongeren and Michael S. Bennington and Martin Lutz and Sally Brooker and Charles Romain and Arnaud Thevenon},
  howpublished = {ChemRxiv},
  year = {2026},
  month = sep,
  doi = {10.26434/chemrxiv.15009526/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009526/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Conformational control for selective CO2-to-isocyanate conversion in a series of dizinc macrocycle complexes
AU  - Timo Q. Hokke
AU  - Lars Killian
AU  - Dylan van Tongeren
AU  - Michael S. Bennington
AU  - Martin Lutz
AU  - Sally Brooker
AU  - Charles Romain
AU  - Arnaud Thevenon
PY  - 2026
DA  - 2026/09/28
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009526/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009526/v1
AB  - 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.
ER  -