Enhanced Catalytic Activity of Oxygen-Tethered Ir-III NHC Complexes in Aqueous Transfer Hydrogenative Reductive Amination Reactions: Experimental Kinetic and Mechanistic Study

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dc.contributor.authorOzbozkurt, Ibrahim Kayahan
dc.contributor.authorGulcemal, Derya
dc.contributor.authorGunnaz, Salih
dc.contributor.authorGokce, Aytac Guerhan
dc.contributor.authorCetinkaya, Bekir
dc.contributor.authorGulcemal, Sueleyman
dc.date.accessioned2019-10-27T10:03:19Z
dc.date.available2019-10-27T10:03:19Z
dc.date.issued2018
dc.departmentEge Üniversitesien_US
dc.description.abstractThe synthesis and characterization of seven new Ir-III complexes containing o-phenoxide or o-naphthoxide chelated N-heterocyclic carbene ligands is reported herein. The crystal structures of six of the complexes have been determined. These complexes efficiently catalyze the transfer hydrogenative reductive amination (RA) of carbonyls and amines in water. Amongst the complexes tested, the introduction of o-naphthoxide on a nitrogen atom of imidazole based NHC ligand greatly increased the catalytic activity. The catalytic system has a broad substrate scope, which allows the synthesis of a variety of amines in excellent yields and with high turnover numbers up to 490 (for ketones) and 14800 (for aldehydes). The mechanism of aqueous RA reaction with an o-aryloxide chelated NHC-Ir-III catalyst has been investigated by NMR spectroscopy and kinetic measurements. These studies suggest that the transfer hydrogenation (TH) is turnover-limited by the hydride formation step. As a result of the H-1 NMR studies, the higher catalytic activity of o-naphthoxide chelated catalyst (3g) over o-phenoxide chelated one (3b) can be attributed partly due to the faster formation of an iridium hydride, the key intermediate in the RA reactions.en_US
dc.description.sponsorshipScientific and Technological Research Council of Turkey (TUBITAK)Turkiye Bilimsel ve Teknolojik Arastirma Kurumu (TUBITAK) [216Z067]; Ege UniversityEge University [2016FEN048, 2017FEN065]; Turkish Academy of Science (TUBA)Turkish Academy of Sciences; Dokuz Eylul UniversityDokuz Eylul University [2010.KB.FEN.13]en_US
dc.description.sponsorshipThe authors thank to The Scientific and Technological Research Council of Turkey (TUBITAK, Grant Number: 216Z067), Ege University (Grant Numbers: 2016FEN048 and 2017FEN065) and The Turkish Academy of Science (TUBA) for the financial support. We gratefully acknowledge to Dr. Stephanie Yip for helpful discussions. The authors also acknowledge Dokuz Eylul University for the use of the Agilent Xcalibur Eos diffractometer (Grant Number: 2010.KB.FEN.13).en_US
dc.identifier.doi10.1002/cctc.201800558
dc.identifier.endpage3604en_US
dc.identifier.issn1867-3880
dc.identifier.issn1867-3899
dc.identifier.issn1867-3880en_US
dc.identifier.issn1867-3899en_US
dc.identifier.issue16en_US
dc.identifier.startpage3593en_US
dc.identifier.urihttps://doi.org/10.1002/cctc.201800558
dc.identifier.urihttps://hdl.handle.net/11454/30099
dc.identifier.volume10en_US
dc.identifier.wosWOS:000443112200033en_US
dc.identifier.wosqualityQ2en_US
dc.indekslendigikaynakWeb of Scienceen_US
dc.language.isoenen_US
dc.publisherWiley-V C H Verlag Gmbhen_US
dc.relation.ispartofChemcatchemen_US
dc.relation.publicationcategoryMakale - Uluslararası Hakemli Dergi - Kurum Öğretim Elemanıen_US
dc.rightsinfo:eu-repo/semantics/closedAccessen_US
dc.subjectN-heterocyclic carbeneen_US
dc.subjectiridiumen_US
dc.subjectreductive aminationen_US
dc.subjectkineticsen_US
dc.subjectmechanismen_US
dc.titleEnhanced Catalytic Activity of Oxygen-Tethered Ir-III NHC Complexes in Aqueous Transfer Hydrogenative Reductive Amination Reactions: Experimental Kinetic and Mechanistic Studyen_US
dc.typeArticleen_US

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