Cooperative anion activation at a cobalt center through ion pairing and ligand design
Tarifa, Luis ; Cano-Asensio, Judit ; López, José A. ; Tejel, Cristina ; Geer, Ana M.
Resumen: Weakly coordinating anions (WCAs) are commonly used to stabilize highvalent, electrophilic transition-metal complexes, owing to their low nucleophilicity and minimal coordinating ability. Here, we present a cobalt platform
supported by a tris(2-pyridyl)(N-picolyl)imidazolidine ligand (Py4Im) that generates a directional, protic cavity for ion pairing. This environment enables a comparative study of BF4 – and PF6⁻, showing that PF6⁻ undergoes fluoride abstraction under mild conditions, while BF4 – remains unreactive unless assisted by a Lewis base. The PF6⁻ activation yields a well-defined CoIII–F complex that acts as an efficient nucleophilic fluoride source. DFT calculations and diffusion NMR experiments highlight the critical role of anion-cation pairing in modulating reactivity, overriding intrinsic thermodynamic preferences. These findings showcase supramolecular control of WCA activation by a late transition metal and provide new design principles for reactivity modulation via counterion selection.
Idioma: Inglés
DOI: 10.1038/s41467-026-69257-8
Año: 2026
Publicado en: Nature communications 17, 1 (2026), 2469 [11 pp.]
ISSN: 2041-1723
Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00
Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2023-148472NB-I00
Financiación: info:eu-repo/grantAgreement/ES/DGA/E50-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIN/RYC2021- 033807-I
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RED2022-134074-T
Tipo y forma: Article (Published version)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. If you remix, transform, or build upon the material, you may not distribute the modified material.
Exportado de SIDERAL (2026-03-26-14:32:15)
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supported by a tris(2-pyridyl)(N-picolyl)imidazolidine ligand (Py4Im) that generates a directional, protic cavity for ion pairing. This environment enables a comparative study of BF4 – and PF6⁻, showing that PF6⁻ undergoes fluoride abstraction under mild conditions, while BF4 – remains unreactive unless assisted by a Lewis base. The PF6⁻ activation yields a well-defined CoIII–F complex that acts as an efficient nucleophilic fluoride source. DFT calculations and diffusion NMR experiments highlight the critical role of anion-cation pairing in modulating reactivity, overriding intrinsic thermodynamic preferences. These findings showcase supramolecular control of WCA activation by a late transition metal and provide new design principles for reactivity modulation via counterion selection.
Idioma: Inglés
DOI: 10.1038/s41467-026-69257-8
Año: 2026
Publicado en: Nature communications 17, 1 (2026), 2469 [11 pp.]
ISSN: 2041-1723
Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00
Financiación: info:eu-repo/grantAgreement/ES/AEI/PID2023-148472NB-I00
Financiación: info:eu-repo/grantAgreement/ES/DGA/E50-23R
Financiación: info:eu-repo/grantAgreement/ES/MCIN/RYC2021- 033807-I
Financiación: info:eu-repo/grantAgreement/ES/MICINN/RED2022-134074-T
Tipo y forma: Article (Published version)
You must give appropriate credit, provide a link to the license, and indicate if changes were made. You may do so in any reasonable manner, but not in any way that suggests the licensor endorses you or your use. You may not use the material for commercial purposes. If you remix, transform, or build upon the material, you may not distribute the modified material. Exportado de SIDERAL (2026-03-26-14:32:15)
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Record created 2026-03-26, last modified 2026-04-07