000170234 001__ 170234
000170234 005__ 20260407115449.0
000170234 0247_ $$2doi$$a10.1038/s41467-026-69257-8
000170234 0248_ $$2sideral$$a148717
000170234 037__ $$aART-2026-148717
000170234 041__ $$aeng
000170234 100__ $$aTarifa, Luis
000170234 245__ $$aCooperative anion activation at a cobalt center through ion pairing and ligand design
000170234 260__ $$c2026
000170234 5060_ $$aAccess copy available to the general public$$fUnrestricted
000170234 5203_ $$aWeakly 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.
000170234 536__ $$9info:eu-repo/grantAgreement/ES/AEI/PID2020-119512GB-I00$$9info:eu-repo/grantAgreement/ES/AEI/PID2023-148472NB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E50-23R$$9info:eu-repo/grantAgreement/ES/MCIN/RYC2021- 033807-I$$9info:eu-repo/grantAgreement/ES/MICINN/RED2022-134074-T
000170234 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttps://creativecommons.org/licenses/by-nc-nd/4.0/deed.es
000170234 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000170234 700__ $$aCano-Asensio, Judit
000170234 700__ $$0(orcid)0000-0003-4500-1974$$aLópez, José A.
000170234 700__ $$0(orcid)0000-0003-3306-0635$$aTejel, Cristina
000170234 700__ $$0(orcid)0000-0003-1115-6759$$aGeer, Ana M.
000170234 773__ $$g17, 1 (2026), 2469 [11 pp.]$$tNature communications$$x2041-1723
000170234 8564_ $$s2170615$$uhttps://zaguan.unizar.es/record/170234/files/texto_completo.pdf$$yVersión publicada
000170234 8564_ $$s2795828$$uhttps://zaguan.unizar.es/record/170234/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000170234 909CO $$ooai:zaguan.unizar.es:170234$$particulos$$pdriver
000170234 951__ $$a2026-03-26-14:32:15
000170234 980__ $$aARTICLE