Artículo
Synthesis and reactivity of half-sandwich (η 5 -C 5 Me 5 )Ir(iii) complexes of a cyclometallated aryl phosphine ligand
Autor/es | Campos Manzano, Jesús
Álvarez González, Eleuterio Carmona Guzmán, Ernesto |
Departamento | Universidad de Sevilla. Departamento de Química Inorgánica |
Fecha de publicación | 2011 |
Fecha de depósito | 2019-07-11 |
Publicado en |
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Resumen | 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 ... 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. |
Identificador del proyecto | CTQ2010-17476
CSD2007-0000 FQM-119 P09-FQM-4832 |
Cita | Campos Manzano, J., Álvarez González, E. y Carmona Guzmán, E. (2011). Synthesis and reactivity of half-sandwich (η 5 -C 5 Me 5 )Ir(iii) complexes of a cyclometallated aryl phosphine ligand. New Journal of Chemistry, 35 (10), 2122-2129. |
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