Rollover Cyclometalation Pathway in Rhodium Catalysis: Dramatic NHC Effects in the C-H Bond Functionalization

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dc.contributor.authorKwak, Jaesungko
dc.contributor.authorOhk, Youhwako
dc.contributor.authorJung, Yousungko
dc.contributor.authorChang, Sukbokko
dc.date.accessioned2013-03-12T15:14:45Z-
dc.date.available2013-03-12T15:14:45Z-
dc.date.created2012-11-30-
dc.date.created2012-11-30-
dc.date.issued2012-10-
dc.identifier.citationJOURNAL OF THE AMERICAN CHEMICAL SOCIETY, v.134, no.42, pp.17778 - 17788-
dc.identifier.issn0002-7863-
dc.identifier.urihttp://hdl.handle.net/10203/102684-
dc.description.abstractOrganometallic chelates are readily obtained upon coordination of metal species to multidentate ligands. Because of the robust structural nature, chelation frequently serves as a driving force in the molecular assembly and chemical architecture, and they are used also as an efficient catalyst in numerous reactions. Described herein is the development of a Rh(NHC) catalytic system for the hydroarylation of alkenes and alkynes with 2,2'-bipyridines (bipy) and 2,2'-biquinolines; the most representative chelating molecules. Initially generated (bipy)Rh(NHC) chelates become labile because of the strong trans-effect of N-heterocyclic carbenes, thus weakening a rhodium-pyridyl bond, which is trans to the bound NHC. Subsequent rollover cyclometalation leads to the C-H bond activation, eventually giving rise to double functionalization of chelate molecules. Density functional calculations are in good agreement with our mechanistic proposal based on the experimental data. The present study elucidated for the first time the dramatic NHC effects on the rollover cyclometalation pathway enabling highly efficient and selective bisfunctionalization of 2,2'-bipyridines and 2,2'-biquinolines.-
dc.languageEnglish-
dc.publisherAMER CHEMICAL SOC-
dc.subjectTRANSITION-METAL-COMPLEXES-
dc.subjectN-HETEROCYCLIC CARBENES-
dc.subjectCARBON-HYDROGEN BONDS-
dc.subjectDIRECT ARYLATION-
dc.subjectORTHO-ALKYLATION-
dc.subjectAROMATIC IMINES-
dc.subject(S)-3,3&apos-
dc.subject-DIMETHYL-2,2&apos-
dc.subject-BIQUINOLINE N,N&apos-
dc.subject-DIOXIDE-
dc.subjectINTRAMOLECULAR ACTIVATION-
dc.subjectPLATINUM(II) DERIVATIVES-
dc.subjectPHOTOPHYSICAL PROPERTIES-
dc.titleRollover Cyclometalation Pathway in Rhodium Catalysis: Dramatic NHC Effects in the C-H Bond Functionalization-
dc.typeArticle-
dc.identifier.wosid000310103800076-
dc.identifier.scopusid2-s2.0-84867758270-
dc.type.rimsART-
dc.citation.volume134-
dc.citation.issue42-
dc.citation.beginningpage17778-
dc.citation.endingpage17788-
dc.citation.publicationnameJOURNAL OF THE AMERICAN CHEMICAL SOCIETY-
dc.identifier.doi10.1021/ja308205d-
dc.contributor.localauthorJung, Yousung-
dc.contributor.localauthorChang, Sukbok-
dc.type.journalArticleArticle-
dc.subject.keywordPlusTRANSITION-METAL-COMPLEXES-
dc.subject.keywordPlusN-HETEROCYCLIC CARBENES-
dc.subject.keywordPlusCARBON-HYDROGEN BONDS-
dc.subject.keywordPlusDIRECT ARYLATION-
dc.subject.keywordPlusORTHO-ALKYLATION-
dc.subject.keywordPlusAROMATIC IMINES-
dc.subject.keywordPlus(S)-3,3&apos-
dc.subject.keywordPlus-DIMETHYL-2,2&apos-
dc.subject.keywordPlus-BIQUINOLINE N,N&apos-
dc.subject.keywordPlus-DIOXIDE-
dc.subject.keywordPlusINTRAMOLECULAR ACTIVATION-
dc.subject.keywordPlusPLATINUM(II) DERIVATIVES-
dc.subject.keywordPlusPHOTOPHYSICAL PROPERTIES-
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