BROWSE

Related Scientist

cchf's photo.

cchf
분자활성촉매반응연구단
more info

ITEM VIEW & DOWNLOAD

Why is the Ir(III)-Mediated Amido Transfer Much Faster Than the Rh(III)-Mediated Reaction? A Combined Experimental and Computational Study

DC Field Value Language
dc.contributor.authorYoonsu Park-
dc.contributor.authorHeo J.-
dc.contributor.authorMu-Hyun Baik-
dc.contributor.authorSukbok Chang-
dc.date.available2017-01-20T08:31:36Z-
dc.date.created2016-11-23-
dc.date.issued2016-10-
dc.identifier.issn0002-7863-
dc.identifier.urihttps://pr.ibs.re.kr/handle/8788114/3269-
dc.description.abstractThe mechanism of the Ir(III)- and Rh(III)-mediated C-N coupling reaction, which is the key step for catalytic C-H amidation, was investigated in an integrated experimental and computational study. Novel amidating agents containing a 1,4,2-dioxazole moiety allowed for designing a stoichiometric version of the catalytic C-N coupling reaction and giving access to reaction intermediates that reveal details about each step of the reaction. Both DFT and kinetic studies strongly point to a mechanism where the M(III)-complex engages the amidating agent via oxidative coupling to form a M(V)-imido intermediate, which then undergoes migratory insertion to afford the final C-N coupled product. For the first time, the stoichiometric versions of the Ir- and Rh-mediated amidation reaction were compared systematically to each other. Iridium reacts much faster than rhodium (∼1100 times at 6.7 °C) with the oxidative coupling being so fast that the activation of the initial Ir(III)-complex becomes rate-limiting. In the case of Rh, the Rh-imido formation step is rate-limiting. These qualitative differences stem from a unique bonding feature of the dioxazole moiety and the relativistic contraction of the Ir(V), which affords much more favorable energetics for the reaction. For the first time, a full molecular orbital analysis is presented to rationalize and explain the electronic features that govern this behavior. © 2016 American Chemical Society-
dc.description.uri1-
dc.language영어-
dc.publisherAMER CHEMICAL SOC-
dc.titleWhy is the Ir(III)-Mediated Amido Transfer Much Faster Than the Rh(III)-Mediated Reaction? A Combined Experimental and Computational Study-
dc.typeArticle-
dc.type.rimsART-
dc.identifier.wosid000386540500044-
dc.identifier.scopusid2-s2.0-84992751008-
dc.identifier.rimsid57727ko
dc.date.tcdate2018-10-01-
dc.contributor.affiliatedAuthorYoonsu Park-
dc.contributor.affiliatedAuthorMu-Hyun Baik-
dc.contributor.affiliatedAuthorSukbok Chang-
dc.identifier.doi10.1021/jacs.6b08211-
dc.identifier.bibliographicCitationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.138, no.42, pp.14020 - 14029-
dc.citation.titleJOURNAL OF THE AMERICAN CHEMICAL SOCIETY-
dc.citation.volume138-
dc.citation.number42-
dc.citation.startPage14020-
dc.citation.endPage14029-
dc.date.scptcdate2018-10-01-
dc.description.wostc38-
dc.description.scptc40-
dc.description.journalClass1-
dc.description.journalRegisteredClassscie-
dc.description.journalRegisteredClassscopus-
Appears in Collections:
Center for Catalytic Hydrocarbon Functionalizations(분자활성 촉매반응 연구단) > 1. Journal Papers (저널논문)
Files in This Item:
Why is the Ir(III).pdfDownload

qrcode

  • facebook

    twitter

  • Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.
해당 아이템을 이메일로 공유하기 원하시면 인증을 거치시기 바랍니다.

Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.

Browse