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

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Author
Piers, Warren E.
Smith, Joel D.
Borau-Garcia, Javier
Spasyuk, Denis M.
Accessioned
2016-04-13T07:47:48Z
Available
2016-04-13T07:47:48Z
Issued
2015-07-28
Type
journal article
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Abstract
An 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.
Grantingagency
NSERC
Refereed
Yes
Accepted manuscript deposited April 11, 2016, as per: http://www.nrcresearchpress.com/page/open-access/options
 
Citation
Can. J. Chem. 2016, 94, 293-296
Department
Chemistry
Faculty
Science
Institution
University of Calgary
Publisher
NRC Press
Doi
http://dx.doi.org/10.1139/cjc-2015-0251
http://dx.doi.org/10.11575/PRISM/35411
Uri
http://hdl.handle.net/1880/51143
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