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dc.contributor.authorFidalgo Zorrilla, Jairo 
dc.contributor.authorRuiz Castañeda, Margarita
dc.contributor.authorGarcía Herbosa, Gabriel 
dc.contributor.authorCarbayo Martín, Mª Aránzazu 
dc.contributor.authorJalón, Félix A.
dc.contributor.authorRodríguez, Ana M.
dc.contributor.authorManzano, Blanca R.
dc.contributor.authorEspino Ordóñez, Gustavo 
dc.date.accessioned2024-01-18T08:30:34Z
dc.date.available2024-01-18T08:30:34Z
dc.date.issued2018-11
dc.identifier.issn0020-1669
dc.identifier.urihttp://hdl.handle.net/10259/8383
dc.description.abstractConsidering the interest in processes related to hydrogen storage such as CO2 hydrogenation and formic acid (FA) decomposition, we have synthesized a set of Ir, Rh, or Ru complexes to be tested as versatile precatalysts in these reactions. In relation with the formation of H2 from FA, the possible applicability of these complexes in the transfer hydrogenation (TH) of challenging substrates as quinoline derivatives using FA/formate as hydrogen donor has also been addressed. Bearing in mind the importance of secondary coordination sphere interactions, N,N′ ligands containing NH2 groups, coordinated or not to the metal center, were used. The general formula of the new complexes are [(p-cymene)RuCl(N,N′)]X, X = Cl–, BF4– and [Cp*MCl(N,N′)]Cl, M = Rh, Ir, where the N,N′ ligands are 8-aminoquinoline (HL1), 6-pyridyl-2,4-diamine-1,3,5-triazine (L2) and 5-amino-1,10-phenanthroline (L3). Some complexes are not active or catalyze only one process. However, the complexes [Cp*MCl(HL1)]Cl with M = Rh, Ir are versatile catalysts that are active in hydrogenation of quinolines, FA decomposition, and also in CO2 hydrogenation with the iridium derivative being more active and robust. The CO2 hydrogenation takes place in mild conditions using only 5 bar of pressure of each gas (CO2 and H2). The behavior of some precatalysts in D2O and after the addition of 9 equiv of HCO2Na (pseudocatalytic conditions) has been studied in detail and mechanisms for the FA decomposition and the hydrogenation of CO2 have been proposed. For the Ru, Ir, or Rh complexes with ligand HL1, the amido species with the deprotonated ligand are observed. In the case of ruthenium, the formate complex is also detected. For the iridium derivative, both the amido intermediate and the hydrido species have been observed. This hydrido complex undergoes a process of umpolung D+↔ Ir–D. All in all, the results of this work reflect the active role of −NH2 in the transfer of H+.en
dc.description.sponsorshipWe gratefully acknowledge thefinancial support provided by the Spanish Ministerio de Economía y Competitividad - FEDER (CTQ2014-58812-C2-1-R). M. R.-C. is grateful for the grant from University of Castilla-La Mancha (programa propio).en
dc.format.mimetypeapplication/pdf
dc.language.isoenges
dc.publisherACS Publicationsen
dc.relation.ispartofInorganic Chemistry. 2018, V. 57, n. 22, p. 14186-14198es
dc.subject.otherQuímica inorgánicaes
dc.subject.otherChemistry, Inorganicen
dc.titleVersatile Rh- and Ir-Based Catalysts for CO2Hydrogenation, Formic Acid Dehydrogenation, and Transfer Hydrogenation of Quinolinesen
dc.typeinfo:eu-repo/semantics/articlees
dc.rights.accessRightsinfo:eu-repo/semantics/openAccesses
dc.relation.publisherversionhttps://doi.org/10.1021/acs.inorgchem.8b02164es
dc.identifier.doi10.1021/acs.inorgchem.8b02164
dc.identifier.essn1520-510X
dc.journal.titleInorganic Chemistryen
dc.volume.number57es
dc.issue.number22es
dc.page.initial14186es
dc.page.final14198es
dc.type.hasVersioninfo:eu-repo/semantics/acceptedVersiones


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