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Activation of acetonitrile in [Cp*Ir(eta(3)-CH2CHCHPh)(NCMe)(+): Crystal structures of iridium-amidine, imino-ether, amido, and amide complexes

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dc.contributor.authorChin, CS-
dc.contributor.authorChong, D-
dc.contributor.authorLee, B-
dc.contributor.authorJeong, H-
dc.contributor.authorWon, G-
dc.contributor.authorDo, Y-
dc.contributor.authorPark, YJ-
dc.date.available2021-02-22T16:47:27Z-
dc.date.created2020-09-01-
dc.date.issued2000-02-21-
dc.identifier.issn0276-7333-
dc.identifier.urihttps://scholarworks.sookmyung.ac.kr/handle/2020.sw.sookmyung/16783-
dc.description.abstractReactions of [Cp*Ir(eta(3)-CH2CHCHPh)(NCMe)]OTf (1) with protic amines, alcohols, and water produce amidine complexes [Cp*Ir(eta(3)-CH2CHCHPh)(NH=C(NR2)Me)]OTf (2) (R-2 = (Me)(2) (a), (Me)(H) (b), (i-Pr)(H) (c), (-CH2(CH2)(3)CH2-) (d)), imino-ether complexes [Cp*Ir-(eta(3)-CH2CHCHPh)(NH=C(OR')Me)]OTf (4) (R' = Me (a), Et (b), i-Pr (c)), and amido complex Cp*Ir(eta(3)-CH2CHCHPh)(NHC(=O)Me) (5-K), respectively. The keto form amido complex 5-K undergoes tautomerization to give the enol form complex Cp*Ir(eta(3)-CH2CHCHPh)(N=C(OH)Me) (5-E) in polar solvents. Tertiary amines (NMe3, NEt3) react with 1 in chlorinated solvents (XCl) to give the chloro complex Cp*IrCl(eta(3)-CH2CHCHPh) (3) and quaternary ammonium salts [R3NX]OTf(R = Me, Et and ii = CH2Cl, CH3, CHCl2, CCl3, PhCH2). Crystal structures of 2a, 4a, 5-K, and [Cp*Ir(NH=C(OH)Me)(OH2)(PPh3)]OTf2 (6) have been determined by single-crystal X-ray diffraction analysis, which lead us to suggest hybrid structures, Ir--NH-C(=N+Me2)Me (2a') for 2a and Ir--NH-C(=O+Me)Me (4a') for 4a to some extent. Complexes 2 and 4 react with PPh3 to give an iridium(III) complex [Cp*Ir(eta(3)-CH2CHCHPh)(PPh3)]OTf (7) and the free amidines NH=C(NR2)Me (8) and imino-ethers NH=C(OR')Me (9), respectively. Nitrile complexes I and [Cp*Ir(eta(3)-CH2CHCHPh)(NCCH=CHMe)]OTf(10) catalyze the hydration of the nitriles in the presence of Na2CO3 to produce amides, and the benzonitrile complex [Cp*Ir(eta(3)-CH2CHCHPh)(NCPh)]OTf(ll) catalyzes the methanolysis of benzonitrile in the presence of Na2CO3 to produce NH=C(OMe)Ph. Plausible mechanisms for these catalytic reactions are suggested with the amido and imino-ether complexes such as 4 and 5 being involved.-
dc.language영어-
dc.language.isoen-
dc.publisherAMER CHEMICAL SOC-
dc.subjectX-RAY STRUCTURE-
dc.subjectCOORDINATED NITRILES-
dc.subjectCATALYZED HYDRATION-
dc.subjectLINKAGE ISOMERIZATION-
dc.subjectNUCLEOPHILIC-ATTACK-
dc.subjectAMINES-
dc.subjectWATER-
dc.subjectACRYLONITRILE-
dc.subjectCARBOXAMIDES-
dc.subjectREACTIVITY-
dc.titleActivation of acetonitrile in [Cp*Ir(eta(3)-CH2CHCHPh)(NCMe)(+): Crystal structures of iridium-amidine, imino-ether, amido, and amide complexes-
dc.typeArticle-
dc.contributor.affiliatedAuthorPark, YJ-
dc.identifier.doi10.1021/om9908480-
dc.identifier.scopusid2-s2.0-0001458543-
dc.identifier.wosid000085450800033-
dc.identifier.bibliographicCitationORGANOMETALLICS, v.19, no.4, pp.638 - 648-
dc.relation.isPartOfORGANOMETALLICS-
dc.citation.titleORGANOMETALLICS-
dc.citation.volume19-
dc.citation.number4-
dc.citation.startPage638-
dc.citation.endPage648-
dc.type.rimsART-
dc.type.docTypeArticle-
dc.description.journalClass1-
dc.description.journalRegisteredClassscie-
dc.description.journalRegisteredClassscopus-
dc.relation.journalResearchAreaChemistry-
dc.relation.journalWebOfScienceCategoryChemistry, Inorganic & Nuclear-
dc.relation.journalWebOfScienceCategoryChemistry, Organic-
dc.subject.keywordPlusX-RAY STRUCTURE-
dc.subject.keywordPlusCOORDINATED NITRILES-
dc.subject.keywordPlusCATALYZED HYDRATION-
dc.subject.keywordPlusLINKAGE ISOMERIZATION-
dc.subject.keywordPlusNUCLEOPHILIC-ATTACK-
dc.subject.keywordPlusAMINES-
dc.subject.keywordPlusWATER-
dc.subject.keywordPlusACRYLONITRILE-
dc.subject.keywordPlusCARBOXAMIDES-
dc.subject.keywordPlusREACTIVITY-
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