Systematic Dismantling of a Carefully Designed PCcarbeneP Pincer Ligand via C-C Bond Activations at an Iridium Centre

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dc.contributor.authorPiers, Warren E.
dc.contributor.authorSmith, Joel D.
dc.contributor.authorBorau-Garcia, Javier
dc.contributor.authorSpasyuk, Denis M.
dc.date.accessioned2016-04-13T07:47:48Z
dc.date.available2016-04-13T07:47:48Z
dc.date.issued2015-07-28
dc.descriptionAccepted manuscript deposited April 11, 2016, as per: http://www.nrcresearchpress.com/page/open-access/optionsen_US
dc.description.abstractAn electron-rich PCsp2P ligand, incorporating N,N-dimethylamino groups para to the anchoring carbene donor of the ligand, was prepared and coordinated to iridium, producing the iridium carbene chloride 2. This species undergoes facile reaction with N2O to afford an iridaepoxide complex, 3, in which an oxygen atom has been transferred to the Ir=C bond. The rate of this reaction is significantly faster than that observed for the less electron rich, unsubstituted ligand. However, further reaction of 3 involving cleavage of one of the ligand C–C bonds was observed, producing the bis-phosphine chorido complex 4. This process was accelerated by the presence of H2. Heating 4 under H2 resulted in hydrogenolysis of the ortho-metalated phosphine ligand to give a hydrido complex (5) and decarbonylation of the acyl phosphine ligand to give, finally, Vaska’s complex analog 6. All compounds were fully characterized, and the sequence represents the dismantling of the PCsp2P ligand framework.en_US
dc.description.grantingagencyNSERCen_US
dc.description.refereedYesen_US
dc.identifier.citationCan. J. Chem. 2016, 94, 293-296en_US
dc.identifier.doi10.1139/cjc-2015-0251
dc.identifier.doihttp://dx.doi.org/10.11575/PRISM/35411
dc.identifier.urihttp://hdl.handle.net/1880/51143
dc.language.isoenen_US
dc.publisherNRC Pressen_US
dc.publisher.departmentChemistryen_US
dc.publisher.facultyScienceen_US
dc.publisher.institutionUniversity of Calgaryen_US
dc.titleSystematic Dismantling of a Carefully Designed PCcarbeneP Pincer Ligand via C-C Bond Activations at an Iridium Centreen_US
dc.typejournal article
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