Efficient Homogeneous Hydridoirida-β-Diketone-Catalyzed Methanolysis of Ammonia-Borane for Hydrogen Release in Air. Mechanistic Insights
dc.contributor.author | Bustos Rosas, Itxaso | |
dc.contributor.author | Freixa Fernández, Zoraida | |
dc.contributor.author | Pazos Pérez, Ariadna | |
dc.contributor.author | Mendicute Fierro, Claudio | |
dc.contributor.author | Garralda Hualde, María Angeles | |
dc.date.accessioned | 2022-01-17T12:57:51Z | |
dc.date.available | 2022-01-17T12:57:51Z | |
dc.date.issued | 2021-08-20 | |
dc.identifier.citation | European Journal of Inorganic Chemistry 31 : 3131-3138 (2021) | es_ES |
dc.identifier.issn | 1434-1948 | |
dc.identifier.issn | 1099-0682 | |
dc.identifier.uri | http://hdl.handle.net/10810/55016 | |
dc.description.abstract | The hydridoirida-beta-diketone [(IrH{(PPh2(o-C6H4CO))(2)H})(2)(mu-Cl)][BF4] (2) has been used as a homogeneous catalyst for the methanolysis of ammonia-borane to release up to 3 equivalents of hydrogen in the presence of air. With catalyst loadings as low as 0.2 mol%, ammonia-borane undergoes methanolysis within 6 min at 30 degrees C, with TOF50% of 320 mol(H2) .mol(Ir)(-1).min(-1), or within 80 s at 60 degrees C, with an excellent TOF50% of 1991 mol(H2).mol(Ir)(-1).min(-1), and maintains its catalytic activity in consecutive runs. Triethylamine-borane fails to undergo methanolysis. Kinetic studies indicate first-order dependence on substrate and on catalyst concentration and suggest cleavage of the solvent O-H bond being involved in the rate determining step of the reaction. In methanol solution 2 forms cationic [IrH(MeOH){(PPh2(o-C6H4CO))(2)H}](+) (3) and reacts with Me3N-BH3 to afford a hydridoirida-beta-diketone [IrH(Me3NBH3){(PPh2(o-C6H4CO))(2)H}](+) (4), with the borane adduct eta(1)-coordinated to iridium. Compound [4][BAr4F] shows dynamic behaviour in solution due to exchange of bridging and terminal B-H bonds. A multinuclear NMR study of the catalyzed reaction shows the formation of two ammonia-methoxyborane adduct intermediates, H3N-BH2(OCH3) and H3N-BH(OCH3)(2), and an iridium species proposed of the hydridodiacyl type [IrH(H3NBH3-x(OCH3)(x))(PPh2(o-C6H4CO))(2)] with a coordinated borane adduct. On account of experimental evidence, a simplified catalytic cycle is suggested for the methanolysis of AB to release hydrogen. | es_ES |
dc.description.sponsorship | Partial financial support by Ministerio de Economia y Competitividad MINECO/FEDER (CTQ2015-65268-C2-1-P and PID2019-111281GB-I00), Gobierno Vasco (GIC 18/143 and IT1180-19) Universidad del Pais Vasco (UPV/EHU) and Diputacion Foral de Gipuzkoa are gratefully acknowledged. I. B. acknowledges support by UPV/EHU. | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | Wiley | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/CTQ2015-65268-C2-1-P | es_ES |
dc.relation | info:eu-repo/grantAgreement/MINECO/PID2019-111281GB-I00 | es_ES |
dc.rights | info:eu-repo/semantics/openAccess | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by/3.0/es/ | * |
dc.subject | ammoniaborane | es_ES |
dc.subject | hydrogen releaseIrida-beta-diketones | es_ES |
dc.subject | methanolysis | es_ES |
dc.subject | sodium-borohydride | es_ES |
dc.subject | amine-boranes | es_ES |
dc.subject | bond activation | es_ES |
dc.subject | dehydrogenation | es_ES |
dc.subject | hydrolysis | es_ES |
dc.subject | generation | es_ES |
dc.subject | nanoparticles | es_ES |
dc.subject | coordination | es_ES |
dc.subject | complexes | es_ES |
dc.subject | dehydropolymerization | es_ES |
dc.title | Efficient Homogeneous Hydridoirida-β-Diketone-Catalyzed Methanolysis of Ammonia-Borane for Hydrogen Release in Air. Mechanistic Insights | es_ES |
dc.type | info:eu-repo/semantics/article | es_ES |
dc.rights.holder | 2021The Authors.EuropeanJournalof InorganicChemistrypublishedbyWiley-VCHGmbH.Thisis an openaccessarticleunderthe termsof theCreativeCommonsAttributionLicense,whichpermitsuse,distributionandreproductionin any medium,providedthe originalworkis properlycited. | es_ES |
dc.rights.holder | Atribución 3.0 España | * |
dc.relation.publisherversion | https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202100318 | es_ES |
dc.identifier.doi | 10.1002/ejic.202100318 | |
dc.departamentoes | Química aplicada | es_ES |
dc.departamentoeu | Kimika aplikatua | es_ES |
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Except where otherwise noted, this item's license is described as 2021The Authors.EuropeanJournalof InorganicChemistrypublishedbyWiley-VCHGmbH.Thisis an openaccessarticleunderthe termsof theCreativeCommonsAttributionLicense,whichpermitsuse,distributionandreproductionin any medium,providedthe originalworkis properlycited.