Iridium complexes of perimidine-based N-heterocyclic carbene pincer ligands via aminal C–H activation

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dc.contributor.authorHill, Anthony
dc.contributor.authorMa, Chenxi
dc.contributor.authorMcQueen, Caitlin
dc.contributor.authorWard, Jas
dc.date.accessioned2019-06-27T04:16:46Z
dc.date.issued2018
dc.date.updated2019-03-24T07:20:43Z
dc.description.abstractThe reactions of N,N′-bis(phosphinomethyl)dihydroperimidine pro-ligands H2C(NCH2PR2)2C10H6-1,8 (R = Ph 1a, R = Cy 1b) with iridium(I) substrates have been investigated and shown to readily result in chelate-assisted C–H activation processes. The reaction of 1b with [Ir2Cl2(COE)4] (COE = cyclo-octene) affords the 18-electron iridium(III) dihydrido complex [IrH2Cl{κ3-C,P,P′-C(NCH2PCy2)2C10H6}], which forms [IrHCl2{κ3-C,P,P′-C(NCH2PCy2)2C10H6}] under acidic (HCl) conditions. In contrast, reaction of 1a with [Ir2Cl2(COD)2] (COD = 1,5-cyclo-octadiene) affords the complex [IrCl(COD){κ2-P,P′-H2C(NCH2PPh2)2C10H6}], thermolysis of which affords cyclo-octene and the pincer-NHC complex [IrCl{κ3-C,P,P′-C(NCH2PPh2)2C10H6}]. The reaction of 1a with two equivalents of [Ir2Cl2(COD)2] provides the binuclear complex [Ir2{μ-H2C(NCH2PPh2)2C10H6}Cl2(COD)2] which is also observed to accumulate and then dissipate during the preceding thermolysis. Related binuclear complexes [M2{μ-H2C(NCH2PPh2)2C10H6}Cl4(η-C5Me5)2] (M = Ir, Rh) which obviate C–H activation were similarly synthesised.en_AU
dc.description.sponsorshipThis work was supported by the Australian Research Council (DP110101611).en_AU
dc.format.mimetypeapplication/pdfen_AU
dc.identifier.issn1477-9226en_AU
dc.identifier.urihttp://hdl.handle.net/1885/164256
dc.language.isoen_AUen_AU
dc.provenancehttps://v2.sherpa.ac.uk/id/publication/18010..."The Accepted Version can be archived in a Non-Commercial Repository. 12 months embargo" from SHERPA/RoMEO site (as at 11/12/2020).
dc.publisherRoyal Society of Chemistryen_AU
dc.relationhttp://purl.org/au-research/grants/arc/DP110101611en_AU
dc.rights© The Royal Society of Chemistry 2018en_AU
dc.sourceDalton Transactionsen_AU
dc.titleIridium complexes of perimidine-based N-heterocyclic carbene pincer ligands via aminal C–H activationen_AU
dc.typeJournal articleen_AU
dcterms.accessRightsOpen Access
local.bibliographicCitation.issue5en_AU
local.bibliographicCitation.lastpage1587en_AU
local.bibliographicCitation.startpage1577en_AU
local.contributor.affiliationHill, Anthony, College of Science, ANUen_AU
local.contributor.affiliationMa, Chenxi, College of Science, ANUen_AU
local.contributor.affiliationMcQueen, Caitlin, College of Science, ANUen_AU
local.contributor.affiliationWard, James, College of Science, ANUen_AU
local.contributor.authoremailrepository.admin@anu.edu.auen_AU
local.contributor.authoruidHill, Anthony, u4030185en_AU
local.contributor.authoruidMa, Chenxi, u5013394en_AU
local.contributor.authoruidMcQueen, Caitlin, u4223499en_AU
local.contributor.authoruidWard, James, u4431856en_AU
local.description.notesImported from ARIESen_AU
local.identifier.absfor030207 - Transition Metal Chemistryen_AU
local.identifier.absfor030204 - Main Group Metal Chemistryen_AU
local.identifier.absfor039904 - Organometallic Chemistryen_AU
local.identifier.absseo970106 - Expanding Knowledge in the Biological Sciencesen_AU
local.identifier.absseo970103 - Expanding Knowledge in the Chemical Sciencesen_AU
local.identifier.ariespublicationu5786633xPUB35en_AU
local.identifier.citationvolume47en_AU
local.identifier.doi10.1039/c7dt04572gen_AU
local.identifier.uidSubmittedByu5786633en_AU
local.publisher.urlhttps://www.rsc.org/en_AU
local.type.statusAccepted Versionen_AU

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