Experimental and Computational Studies on the Iridium Activation of Aliphatic and Aromatic C-H Bonds of Alkyl Aryl Ethers and Related Molecules
| Autor: | Margarita Paneque, Ernesto Carmona, Gregori Ujaque, Agustí Lledós, Kurt Mereiter, Eleuterio Álvarez, Laura L. Santos, Patricia Lara, Manuel L. Poveda, Salvador Moncho, José E. V. Valpuesta |
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| Rok vydání: | 2009 |
| Předmět: |
chemistry.chemical_classification
Chemistry Hydride Aryl Organic Chemistry General Chemistry Anisole Hydride complexes Iridium Medicinal chemistry Catalysis chemistry.chemical_compound Density functional calculations Electrophile Carbenes Molecule Organic chemistry C-H activation Carbene Derivative (chemistry) Alkyl |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | 12 páginas, 7 figuras, 1 tabla, 6 esquemas Reaction of the IrIII complex [(TpMe2)Ir(C6H5)2(N2)] (1⋅N2) with ortho-cresol (2-methylphenol) occurs with cleavage of the O-H and two C(sp3)-H bonds of the phenol and formation of the electrophilic hydride alkylidene derivative [(TpMe2)Ir(H){=C(H)C6H4-o-O}] (2). The analogous reaction of 2-ethylphenol gives a related product 3. Both 2 and 3 have been shown to be identical to the minor, unidentified products of the already reported reactions of 1 with anisole and phenetole, respectively. Thus, in addition to the route that leads to the known heteroatom-stabilized hydride carbene [(TpMe2)Ir(H){=C(H)OC6H4- o-}] (B), anisole can react with 1 with cleavage of the O=CH3 bond and formation of a new carbon–carbon bond. In contrast, only C-H bond-activation products with structures akin to B result from 1⋅N2 and 3,5-dimethylanisole (complex 8) or 4-fluoroanisole (9). Using anisole as a model, a computational study of the triple C-H bond activation (two aliphatic C-H bonds plus an ortho-metalation reaction) that is responsible for the formation of these heteroatom-stabilized hydride carbenes has been undertaken. We thank the Spanish Ministerio de Ciencia e Innovación (projects CTQ2007-62814, CTQ2008-06866-C02-01/BQU, and Consolider Ingenio-2010 CSD2007-00006) and the Junta de Andalucía (project FQM672) for financial support (FEDER support). S.M. and J.E.V.V. thank the MICINN and MEC for research grants. |
| Databáze: | OpenAIRE |
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