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Homodinuclear Rhˡ and Irˡ Complexes Derived from Imidazolium-Benzimidazolates

dc.date.accessioned2021-06-17T10:18:34Z
dc.date.available2021-06-17T10:18:34Z
dc.date.issued2020-11-19
dc.identifierdoi:10.17170/kobra-202106094099
dc.identifier.urihttp://hdl.handle.net/123456789/12934
dc.description.sponsorshipGefördert im Rahmen des Projekts DEALger
dc.language.isoengeng
dc.rightsNamensnennung 4.0 International*
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subjectcarbeneseng
dc.subjectcoordination modeseng
dc.subjectIridium; Rhodiumeng
dc.subjectx-ray diffractioneng
dc.subject.ddc540
dc.titleHomodinuclear Rhˡ and Irˡ Complexes Derived from Imidazolium-Benzimidazolateseng
dc.typeAufsatz
dcterms.abstractThe reactions of [M(μ-Cl)(COD)]2 (M=Rh, Ir) with the conjugated mesomeric betaines 2-(3-methyl-1-imidazolium)-benzimidazolate (1aH), 2-(3-isopropyl-1-imidazolium)-benzimidazolate (1bH) and 2-(3-tert-butyl-1-imidazolium)-benzimidazolate (1cH) in equilibrium with their carbenic tautomers 1’aH, 1’bH and 1’cH were investigated. In the case of 1aH and 1bH, the homodinuclear complexes [MCl(COD){M(μ-1’a)(COD)}] and [MCl(COD){M(μ-1’b)(COD)}] were obtained, whose anionic NHC ligand 1’a− or 1’b− bridges the metal centres in a κ1N : κ1N mode, while binding the M(COD) moiety in a C,N-chelating mode. For M=Ir, [IrCl(COD){Ir(μ-1’’b)(COD)}] containing the “abnormal” NHC isomer 1’’b− was observed as a side product. In the case of 1’cH, [{RhCl(COD)}2(μ-1cH)] containing a κ1N : κ1N benzimidazolato ligand was obtained for M=Rh, while for M=Ir the reaction furnished [IrCl(COD){Ir(μ-1’’c)(COD)}], which contains the anionic “abnormal” NHC ligand 1’’c−. This difference in behaviour is rationalised by the propensity of iridium(I) for oxidative addition, which in the present case involves a C−H bond of the dangling formamidium unit of [{IrCl(COD)}2(μ-1cH)] to afford [IrICl(COD){IrIIIHCl(μ-1’’c)(COD)}], followed by reductive elimination of HCl. The crystal structures of the new complexes were determined by single-crystal X-ray diffraction, except for [IrCl(COD){Ir(μ-1’a)(COD)}], where by serendipity the closely related mononuclear complex [Ir(1’a)(COD)] was structurally characterised instead.eng
dcterms.accessRightsopen access
dcterms.creatorKureja, Kunal
dcterms.creatorZinke, Julian
dcterms.creatorBruhn, Clemens
dcterms.creatorSiemeling, Ulrich
dc.relation.doidoi:10.1002/zaac.202000394
dc.subject.swdCarbeneger
dc.subject.swdChemische Bindungger
dc.subject.swdIridiumger
dc.subject.swdRhodiumger
dc.subject.swdRöntgenbeugungger
dc.title.subtitleDedicated to Prof. Christoph Janiak on the Occasion of his 60th Birthdayeng
dc.type.versionpublishedVersion
dcterms.source.identifiereissn:1521-3749
dcterms.source.issueIssue 11
dcterms.source.journalZeitschrift für anorganische und allgemeine Chemie (ZAAC) = Journal of inorganic and general chemistryger
dcterms.source.pageinfo1173-1181
dcterms.source.volumeVolume 647
kup.iskupfalse


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Except where otherwise noted, this item's license is described as Namensnennung 4.0 International