dc.contributor.author | Bustos Rosas, Itxaso | |
dc.contributor.author | Seco Botana, José Manuel | |
dc.contributor.author | Rodríguez Diéguez, Antonio | |
dc.contributor.author | Garralda Hualde, María Angeles | |
dc.contributor.author | Mendicute Fierro, Claudio | |
dc.date.accessioned | 2024-01-26T16:37:54Z | |
dc.date.available | 2024-01-26T16:37:54Z | |
dc.date.issued | 2022-12-01 | |
dc.identifier.citation | Organometallics 41(23) : 3654-3663 (2022) | es_ES |
dc.identifier.issn | 0276-7333 | |
dc.identifier.issn | 1520-6041 | |
dc.identifier.uri | http://hdl.handle.net/10810/64389 | |
dc.description.abstract | Aliphatic diamines [(H2N(CH2)nNHR) (a–d) n = 2: R = H (a), R = CH3 (b), R = C2H5 (c), n = 3, R = H (d) or rac-2-(aminomethyl)piperidine (e)] react with [IrH(Cl){(PPh2(o-C6H4CO))2H}] in THF to afford ketoimine complexes [IrH(Cl){(PPh2(o-C6H4CO))(PPh2(o-C6H4CN(CH2)nNHR))H}] (2a–2d) or [IrH(Cl){(PPh2(o-C6H4CO))(PPh2(o-C6H4CNCH2(C5H9NH)))H}] (2e), containing a bridging N–H···O hydrogen bond and a dangling amine. Complex 2e consists of an almost equimolar mixture of two diastereomers. In protic solvents, the dangling amine in complexes 2 displaces chloride to afford cationic acyl-iminium compounds, [IrH(PPh2(o-C6H4CO))(PPh2(o-C6H4CNH(CH2)nNHR))]X (3a–3d, X = Cl) or [IrH(PPh2(o-C6H4CO))(PPh2(o-C6H4CNHCH2(C5H9NH)))]Cl (3e) and (4a–4b, X = ClO4), with new hemilabile terdentate PCNamine ligands adopting a facial disposition. Complexes 3 contain the corresponding phosphorus atom trans to hydride and the amine fragment trans to acyl, while complexes 4 contain the amine trans to hydride. 3b and 4b consist of 80:20 and 95:5 mixtures of diastereomers, respectively, while 3e contains a 65:35 mixture. In the presence of KOH, intermediate cationic acyl-iminium complexes 3 transform into neutral acyl-imine [IrH(PPh2(o-C6H4CO))(PPh2(o-C6H4CN(CH2)nNHR))] derivatives (5) with retention of the stereochemistry. Single-crystal X-ray diffraction analysis was performed on 2a, [3a]Cl, [3b]Cl, [4a]ClO4, and 5b. Complexes 2, 3, and 5 catalyze the methanolysis of ammonia-borane under air to release hydrogen. The highest activity is observed for ketoimine complexes 2. | es_ES |
dc.description.sponsorship | Partial financial support by Ministerio de Economía y Competitividad MINECO/FEDER (CTQ2015-65268-C2-1-P and PID2019- 111281GB-I00), Gobierno Vasco (GIC 18/143 and IT1180-19) Universidad del País Vasco (UPV/EHU), and Diputación Foral de Gipuzkoa are gratefully acknowledged. I. B. acknowledges support by UPV/EHU. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | ACS | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/4.0/ | * |
dc.subject | Amines, Anions, Hydrogen, Ligands, Molecular structure | es_ES |
dc.subject | amines | es_ES |
dc.subject | anions | es_ES |
dc.subject | Hydrogen | es_ES |
dc.subject | ligands | es_ES |
dc.subject | molecular structure | es_ES |
dc.title | Formation of Irida-β-ketoimines and PCNamine-Ir(III) Complexes by Reacting Irida-β-diketones with Aliphatic Diamines: Catalytic Activity in Hydrogen Release by Methanolysis of H3N–BH3 | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | © 2022 American Chemical Society. This publication is licensed under
CC-BY 4.0. | es_ES |
dc.relation.publisherversion | https://pubs.acs.org/doi/full/10.1021/acs.organomet.2c00451 | es_ES |
dc.identifier.doi | 10.1021/acs.organomet.2c00451 | |
dc.departamentoes | Química aplicada | es_ES |
dc.departamentoeu | Kimika aplikatua | es_ES |