Systematic dismantling of a carefully designed PCcarbeneP pincer ligand via C–C bond activations at an iridium centre
| Autor: | Denis M. Spasyuk, Warren E. Piers, Javier Borau-Garcia, Joel D. Smith |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Ligand Organic Chemistry Decarbonylation chemistry.chemical_element Bridging ligand General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Medicinal chemistry Catalysis 0104 chemical sciences chemistry.chemical_compound chemistry Hydrogenolysis Iridium Pincer ligand Carbene Phosphine |
| Zdroj: | Canadian Journal of Chemistry. 94:293-296 |
| ISSN: | 1480-3291 0008-4042 |
| DOI: | 10.1139/cjc-2015-0251 |
| Popis: | 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. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|