{"@context":{"@vocab":"https://cir.nii.ac.jp/schema/1.0/","rdfs":"http://www.w3.org/2000/01/rdf-schema#","dc":"http://purl.org/dc/elements/1.1/","dcterms":"http://purl.org/dc/terms/","foaf":"http://xmlns.com/foaf/0.1/","prism":"http://prismstandard.org/namespaces/basic/2.0/","cinii":"http://ci.nii.ac.jp/ns/1.0/","datacite":"https://schema.datacite.org/meta/kernel-4/","ndl":"http://ndl.go.jp/dcndl/terms/","jpcoar":"https://github.com/JPCOAR/schema/blob/master/2.0/"},"@id":"https://cir.nii.ac.jp/crid/1363388844117536896.json","@type":"Article","productIdentifier":[{"identifier":{"@type":"DOI","@value":"10.1021/ja8063028"}},{"identifier":{"@type":"URI","@value":"https://pubs.acs.org/doi/pdf/10.1021/ja8063028"}},{"identifier":{"@type":"PMID","@value":"19007215"}}],"dc:title":[{"@value":"C−H Bond Activation of Heteroarenes Mediated by a Half-Sandwich Iron Complex of N-Heterocyclic Carbene"}],"description":[{"notation":[{"@value":"Half-sandwich iron complexes of N-heterocyclic carbenes, Cp*Fe(L(R))Cl (2a; L(Mes) = 1,3-dimesityl-imidazol-2-ylidene, 2b; L(iPr) = 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene, Cp* = eta(5)-C5Me5), have been synthesized by the reaction of Cp*Fe{N(SiMe3)2} (1) with the corresponding imidazolium salts. Treatment of 2a with either methyllithium or phenyllithium replaces the chloride with either a methyl or a phenyl group, generating Cp*Fe(L(Mes))R (3a; R = Me, 3b; R = Ph). These complexes, in turn, undergo cyclometalation at elevated temperatures, and Cp*Fe{kappa2-(C,C)-L'(Mes)} (4; L'(Mes) = CH2C6H2-3,5-Me2-2-(3-mesityl-imidazol-2-ylidene-1-yl)) was isolated. On the other hand, methylation of 2b at room temperature leads directly to the formation of a cyclometalated complex, Cp*Fe{kappa2-(C,C)-L'(iPr)} (6; L'(iPr) = CH2CH(CH3)(3-isopropyl-4,5-dimethylimidazol-2-ylidene-1-yl)). The Fe(II) center of 6 traps atmospheric dinitrogen reversibly to produce a dinuclear end-on N2 complex [Cp*Fe{kappa2-(C,C)-L'(iPr)}]2(mu-eta(1):eta(1)-N2) (7). Complex 6 also promotes C-H bond activation of thiophene, furan, benzothiophene, and benzofuran at room temperature. In these reactions, C-H bond cleavage occurred exclusively at the 2-position of the rings, generating Cp*Fe(L(iPr))(2-C4H3E) (8; E = S, 9; E = O) and Cp*Fe(L(iPr))(2-C8H5E) (10; E = S, 11; E = O), while C-H cleavage took place mainly at the 4-position in the case of pyridine. Coupling reactions between heteroarenes and catecholborane (HBcat) can be carried out by treatment of 6 with heteroarenes followed by the addition of excess HBcat, giving rise to 2-boryl-heteroarenes and the borohydride complex Cp*Fe(L(iPr))(H2Bcat) (14)."}]}],"creator":[{"@id":"https://cir.nii.ac.jp/crid/1383388844117536898","@type":"Researcher","foaf:name":[{"@value":"Yasuhiro Ohki"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Graduate School of Science, and Research Center for Meterials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1420001326236325888","@type":"Researcher","personIdentifier":[{"@type":"KAKEN_RESEARCHERS","@value":"80595330"},{"@type":"NRID","@value":"1000080595330"},{"@type":"NRID","@value":"9000018544266"},{"@type":"NRID","@value":"9000323295606"},{"@type":"NRID","@value":"9000411769903"},{"@type":"RESEARCHMAP","@value":"https://researchmap.jp/tHatanaka"}],"foaf:name":[{"@value":"Tsubasa Hatanaka"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Graduate School of Science, and Research Center for Meterials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan"}]},{"@id":"https://cir.nii.ac.jp/crid/1383388844117536896","@type":"Researcher","foaf:name":[{"@value":"Kazuyuki Tatsumi"}],"jpcoar:affiliationName":[{"@value":"Department of Chemistry, Graduate School of Science, and Research Center for Meterials Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan"}]}],"publication":{"publicationIdentifier":[{"@type":"PISSN","@value":"00027863"},{"@type":"EISSN","@value":"15205126"}],"prism:publicationName":[{"@value":"Journal of the American Chemical Society"}],"dc:publisher":[{"@value":"American Chemical Society (ACS)"}],"prism:publicationDate":"2008-11-14","prism:volume":"130","prism:number":"50","prism:startingPage":"17174","prism:endingPage":"17186"},"reviewed":"false","url":[{"@id":"https://pubs.acs.org/doi/pdf/10.1021/ja8063028"}],"createdAt":"2008-11-14","modifiedAt":"2023-03-07","relatedProduct":[{"@id":"https://cir.nii.ac.jp/crid/1360002214681060736","@type":"Article","resourceType":"学術雑誌論文(journal article)","relationType":["isReferencedBy"],"jpcoar:relatedTitle":[{"@value":"New Synthetic Routes to Metal‐Sulfur Clusters Relevant to the Nitrogenase Metallo‐Clusters"}]},{"@id":"https://cir.nii.ac.jp/crid/1360002216612517120","@type":"Article","resourceType":"学術雑誌論文(journal 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