Isomerization of a cationic (η5-C5Me5)Ir(III) complex involving remote C–C and C–H bond formation
The reactivity of an unsaturated, cationic (C5Me5)Ir(III) complex (2(Xyl)þ) bearing the xylyl-substituted terphenyl phosphine PMe2ArXyl2 (ArXyl2 = C6H3-2,6-(C6H3-2,6-Me2)2) towards triethylamine (NEt3) is studied and compared to our previous investigations based on the related complex 2(Dipp)þ conta...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2021 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/247571 |
| Acceso en línea: | http://hdl.handle.net/10261/247571 |
| Access Level: | acceso abierto |
| Palabra clave: | Iridium DFT Terphenyl phosphine Organometallic C5Me5 |
| Sumario: | The reactivity of an unsaturated, cationic (C5Me5)Ir(III) complex (2(Xyl)þ) bearing the xylyl-substituted terphenyl phosphine PMe2ArXyl2 (ArXyl2 = C6H3-2,6-(C6H3-2,6-Me2)2) towards triethylamine (NEt3) is studied and compared to our previous investigations based on the related complex 2(Dipp)þ containing the bulkier phosphine PMe2ArDipp2 (ArDipp2 = C6H3-2,6-(C6H3-2,6-iPr2)2). Low-temperature multinuclear NMR studies support the formation of a C–C bond between the deprotonated C5Me5 ligand and a flanking xylyl ring of the phosphine, which becomes dearomatized (complex 4(Xyl)þ). Interestingly, this complex presents divergent reactivity relative to the bulkier diisopropylphenyl counterpart, undergoing formal addition of HCl to yield complex 5 (Xyl)þ, isomeric to the starting complex 2(Xyl)þ. These transformations are rationalized by means of Density Functional Theory (DFT) calculations |
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