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2025-02-20T19:13:27Z urn:hdl:10324/75092 Assessing the cooperating ability of 6‐hydroxypicolinic acid and pyridyl‐amide ligands in palladium‐mediated C−H activation Pinilla Martín, Cintya Albéniz Jiménez, Ana Carmen Química Producción Científica The behavior of 6-hydroxypicolinic acid (pic-6-OH) and pyridyl- amides as cooperating ligands in the C- H activation of arenes has been studied experimentally. When deprotonated, both compounds are chelating ligands and bear either a pyridone moiety or an N-acyl substituent that can assist the C-H cleavage in the same way as the successful bipyridone ligands and MPAAs do. In addition, they are easily available, commercially or via straightforward syntheses. Palladium complexes of formula (NBu4)[Pd(k2-O, N-pic-6-O)(C6F5)py] (2) and [Pd(k2-N, N- py-CH2N(COCF3)(C6F5)py] (6) have been synthesized and their decomposition in the presence of an arene gives the C6F5-arene coupling product, showing that the ligands enable the C-H activation of the arene (arene = pyridine, toluene, ethyl ben- zoate). The amount of C6F5-arene products observed leads to the following trend in cooperating ability: pic-6-OH > pyridyl- amide. DFT calculations on the pyridine activation are consis- tent with the experimental findings. The C-H activation does not occur for the isomeric complex (NBu4)[Pd(k2-O, N-pic-4- O)(C6F5)py] (4) with the pyridone oxygen far from the metal, showing the involvement of this moiety in the C-H cleavage. The performance of these ligands in the direct arylation of arenes has been evaluated. 2025-02-20T19:13:27Z 2025-02-20T19:13:27Z 2024 info:eu-repo/semantics/article European Journal of Inorganic Chemistry, 2024, vol. 27, n. 17, e202400076 1434-1948 https://uvadoc.uva.es/handle/10324/75092 10.1002/ejic.202400076 e202400076 17 European Journal of Inorganic Chemistry 27 1099-0682 eng https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202400076 info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by-nc-nd/4.0/ Attribution-NonCommercial-NoDerivatives 4.0 Internacional Wiley