Synthesis and reactivity of half-sandwich (η 5 -C 5 Me 5 )Ir(iii) complexes of a cyclometallated aryl phosphine ligand
Reaction of the Ir(iii) dimer [(η 5 -C 5 Me 5 )IrCl 2 ] 2 with PMeXyl 2 (Xyl = 2,6-C 6 H 3 Me 2 ), in the presence of the poorly coordinating base 2,2,6,6-tetramethyl piperidine, gives a chloride complex 1-Cl, resulting from hydrogen chloride elimination involving one of the phosphine benzylic hydro...
| Autores: | , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión enviada para evaluación y publicación |
| Fecha de publicación: | 2011 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/88012 |
| Acceso en línea: | https://hdl.handle.net/11441/88012 https://doi.org/10.1039/c1nj20244h |
| Access Level: | acceso abierto |
| Sumario: | Reaction of the Ir(iii) dimer [(η 5 -C 5 Me 5 )IrCl 2 ] 2 with PMeXyl 2 (Xyl = 2,6-C 6 H 3 Me 2 ), in the presence of the poorly coordinating base 2,2,6,6-tetramethyl piperidine, gives a chloride complex 1-Cl, resulting from hydrogen chloride elimination involving one of the phosphine benzylic hydrogen atoms and concomitant cyclometallation. Related compounds containing other halide or pseudohalide ligands, 1-Br, 1-Cl, 1-SCN, can be made, the latter featuring S-coordination of the ambidentate thiocyanate to the soft Ir(iii) Lewis acid centre, as suggested by IR data and demonstrated by X-ray crystallography. Hydride 2-H, and alkyl derivatives 3 (Me) and 4 (CH 2 SiMe 3 ) can also be prepared from 1-Cl and appropriate hydride and alkylating reagents. An interesting H/D exchange chemistry that occurs in the presence of CD 3 OD has been disclosed for 1-Cl, 1-Br and 2-H. For the halide derivatives, deuterium incorporation takes place into the methylene and methyl sites of their cyclometallated ligand, whereas for 2-H only the hydride and methylene (Ir-CH 2 ) protons participate in the exchange, which is strikingly accelerated by catalytic amounts of acids. |
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