000165221 001__ 165221
000165221 005__ 20251219174251.0
000165221 0247_ $$2doi$$a10.1021/acs.inorgchem.5c03962
000165221 0248_ $$2sideral$$a146754
000165221 037__ $$aART-2025-146754
000165221 041__ $$aeng
000165221 100__ $$aGarcía-Abellán, Susana
000165221 245__ $$aHemilability Modulation via Phosphane-Triazole Ligand Design: Impact on Catalytic Formic Acid Dehydrogenation
000165221 260__ $$c2025
000165221 5060_ $$aAccess copy available to the general public$$fUnrestricted
000165221 5203_ $$aTwo novel P–N ligands, 1-[2-(diphenylphosphanyl)ethyl]-1H-benzo-1,2,3-triazole (1) and its N2-isomer (2), were synthesized. Reaction of 1 and 2 with [Ir(μ-Cl)(cod)]2 and [Rh(μ-Cl)(cod)]2 in a 2:1 molar ratio followed by AgBF4 led to the formation of square-planar κ2-P,N complexes, Ir-1, Ir-2, Rh-1 and Rh-2. Density functional theory studies provided insights into the electronic structure and bonding of the complexes. Complex Ir-3 was also prepared for comparison, employing ligand 3, 1-[2-(diphenylphosphanyl)methyl]-1H-benzo-1,2,3-triazole. Variable-temperature NMR studies on [IrCl(cod)(P–N)] complexes revealed fluxional behavior attributed to ligand hemilability. Activation Gibbs free energies (ΔG‡) for the isomerization equilibrium of [IrCl(cod)(PN)] complexes featuring ligands 1, 2 and 3 are 10.24, 10.60, and 8.87 kcal·mol–1, respectively. This enabled us to propose a coordination-ability scale that follows the trend 3 > 1 > 2. The relative activities of the iridium complexes were evaluated in the dehydrogenation of formic acid. Under optimized conditions, in an HCOOH/Et3N mixture, the initial TOFs are 186, 828, and 948 h–1 for Ir-1, Ir-2, and Ir-3, respectively. This indicates that Ir-3, bearing the most strongly coordinating ligand, exhibits the highest catalytic activity, reaching a TON value of 444 after 7 h. This study demonstrates the tunability of the hemilability of benzo-1,2,3-triazole-based P–N ligands and their potential for modulating catalytic activity.
000165221 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-122763NB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00
000165221 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttps://creativecommons.org/licenses/by/4.0/deed.es
000165221 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000165221 700__ $$aPérez-García, Andrea$$uUniversidad de Zaragoza
000165221 700__ $$aBarrena-Espés, Daniel
000165221 700__ $$0(orcid)0000-0003-1707-3022$$aCasado, Miguel A.$$uUniversidad de Zaragoza
000165221 700__ $$0(orcid)0000-0001-6089-6126$$aMunarriz, Julen$$uUniversidad de Zaragoza
000165221 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000165221 700__ $$0(orcid)0000-0003-3144-5320$$aIglesias, Manuel
000165221 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000165221 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000165221 773__ $$g(2025), [14 pp.]$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000165221 8564_ $$s4525666$$uhttps://zaguan.unizar.es/record/165221/files/texto_completo.pdf$$yVersión publicada
000165221 8564_ $$s2938218$$uhttps://zaguan.unizar.es/record/165221/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000165221 909CO $$ooai:zaguan.unizar.es:165221$$particulos$$pdriver
000165221 951__ $$a2025-12-19-14:43:17
000165221 980__ $$aARTICLE