Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance

IThe 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,...

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Autores: Gómez-España, Alejandra, López-Morales, Jorge L., Español-Sanchez, Belinda, García-Orduña, Pilar, Lahoz, Fernando J., Iglesias, Manuel, Fernández-Alvarez, Francisco J.
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2023
País:España
Institución:Universidad de Zaragoza
Repositorio:Zaguán. Repositorio Digital de la Universidad de Zaragoza
OAI Identifier:oai:zaguan.unizar.es:127813
Acceso en línea:http://zaguan.unizar.es/record/127813
Access Level:acceso abierto
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repository_id_str
spelling Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performanceGómez-España, AlejandraLópez-Morales, Jorge L.Español-Sanchez, BelindaGarcía-Orduña, PilarLahoz, Fernando J.Iglesias, ManuelFernández-Alvarez, Francisco J.IThe 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.2023info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionapplication/pdfhttp://zaguan.unizar.es/record/127813reponame:Zaguán. Repositorio Digital de la Universidad de Zaragozainstname:Universidad de ZaragozaInglésinfo:eu-repo/grantAgreement/ES/DGA-FSE/E42-20Rinfo:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00info:eu-repo/semantics/openAccessoai:zaguan.unizar.es:1278132026-05-29T13:59:51Z
dc.title.none.fl_str_mv Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
title Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
spellingShingle Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
Gómez-España, Alejandra
title_short Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
title_full Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
title_fullStr Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
title_full_unstemmed Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
title_sort Iridium-(K2-NSi) catalyzed dehydrogenation of formic acid: effect of auxiliary ligands on the catalytic performance
dc.creator.none.fl_str_mv Gómez-España, Alejandra
López-Morales, Jorge L.
Español-Sanchez, Belinda
García-Orduña, Pilar
Lahoz, Fernando J.
Iglesias, Manuel
Fernández-Alvarez, Francisco J.
author Gómez-España, Alejandra
author_facet Gómez-España, Alejandra
López-Morales, Jorge L.
Español-Sanchez, Belinda
García-Orduña, Pilar
Lahoz, Fernando J.
Iglesias, Manuel
Fernández-Alvarez, Francisco J.
author_role author
author2 López-Morales, Jorge L.
Español-Sanchez, Belinda
García-Orduña, Pilar
Lahoz, Fernando J.
Iglesias, Manuel
Fernández-Alvarez, Francisco J.
author2_role author
author
author
author
author
author
description IThe 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.
publishDate 2023
dc.date.none.fl_str_mv 2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://zaguan.unizar.es/record/127813
url http://zaguan.unizar.es/record/127813
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R
info:eu-repo/grantAgreement/ES/MICINN/PID2021-126212OB-I00
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
eu_rights_str_mv openAccess
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv
publisher.none.fl_str_mv
dc.source.none.fl_str_mv reponame:Zaguán. Repositorio Digital de la Universidad de Zaragoza
instname:Universidad de Zaragoza
instname_str Universidad de Zaragoza
reponame_str Zaguán. Repositorio Digital de la Universidad de Zaragoza
collection Zaguán. Repositorio Digital de la Universidad de Zaragoza
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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