000127813 001__ 127813
000127813 005__ 20241125101157.0
000127813 0247_ $$2doi$$a10.1039/d3dt00744h
000127813 0248_ $$2sideral$$a133799
000127813 037__ $$aART-2023-133799
000127813 041__ $$aeng
000127813 100__ $$aGómez-España, Alejandra
000127813 245__ $$aIridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
000127813 260__ $$c2023
000127813 5060_ $$aAccess copy available to the general public$$fUnrestricted
000127813 5203_ $$aIThe iridium(III) complexes [Ir(H)(Cl)(κ2-NSitBu2)(κ2-bipyMe2)] (2) and [Ir(H)(OTf)(κ2-NSitBu2)(κ2-bipyMe2)] (3) (NSitBu2 = {4-methylpyridine-2-yloxy}ditertbutylsilyl) have been synthesized and characterized including X-ray studies of 3. A comparative study of the catalytic activity of complexes 2, 3, [Ir(H)(OTf)(κ2-NSitBu2)(coe)] (4), and [Ir(H)(OTf)(κ2-NSitBu2)(PCy3)] (5) (0.1 mol%) as catalysts precursors for the solventless formic acid dehydrogenation (FADH) in the presence of Et3N (40 mol%) at 353 K has been performed. The highest activity (TOF5 min ≈ 3260 h−1) has been obtained with 3 at 373 K. However, at that temperature the FTIR spectra show traces of CO together with the desired products (H2 and CO2). Thus, the best performance was achieved at 353 K (TOF5 min ≈ 1210 h−1 and no observable CO). Kinetic studies at variable temperature show that the activation energy of the 3-catalyzed FADH process is 16.76 kcal mol−1. Kinetic isotopic effect (5 min) values of 1.6, 4.5, and 4.2 were obtained for the 3-catalyzed dehydrogenation of HCOOD, DCOOH, and DCOOD, respectively, at 353 K. The strong KIE found for DCOOH and DCOOD evidenced that the hydride transfer from the C–H bond of formic acid to the metal is the rate-determining step of the process.
000127813 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00
000127813 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000127813 590__ $$a3.5$$b2023
000127813 592__ $$a0.697$$b2023
000127813 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b13 / 44 = 0.295$$c2023$$dQ2$$eT1
000127813 593__ $$aInorganic Chemistry$$c2023$$dQ1
000127813 594__ $$a6.6$$b2023
000127813 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000127813 700__ $$aLópez-Morales, Jorge L.
000127813 700__ $$aEspañol-Sanchez, Belinda
000127813 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, Pilar
000127813 700__ $$aLahoz, Fernando J.
000127813 700__ $$0(orcid)0000-0003-3144-5320$$aIglesias, Manuel
000127813 700__ $$0(orcid)0000-0002-0497-1969$$aFernández-Alvarez, Francisco J.$$uUniversidad de Zaragoza
000127813 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000127813 773__ $$g52, 20 (2023), 6722-6729$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000127813 8564_ $$s904069$$uhttps://zaguan.unizar.es/record/127813/files/texto_completo.pdf$$yVersión publicada
000127813 8564_ $$s2390607$$uhttps://zaguan.unizar.es/record/127813/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000127813 909CO $$ooai:zaguan.unizar.es:127813$$particulos$$pdriver
000127813 951__ $$a2024-11-22-12:09:54
000127813 980__ $$aARTICLE