Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand†‡
Ligand exchange reactions have been used for the synthesis of metallacyclic complexes of Ni and Pd of the type [M[upper bond 1 start](CH2CMe2-o-C6[upper bond 1 end]H4)(P–N)], where P–N is the phosphinito-imine ligand P(iPr)2OC(Me)[double bond, length as m-dash]N(2,6-C6H3(iPr)2. The protic acid [H(OE...
| Autores: | , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2012 |
| País: | España |
| Institución: | Universidad de Sevilla (US) |
| Repositorio: | idUS. Depósito de Investigación de la Universidad de Sevilla |
| OAI Identifier: | oai:idus.us.es:11441/79407 |
| Acceso en línea: | https://hdl.handle.net/11441/79407 https://doi.org/10.1039/C2DT31334K |
| Access Level: | acceso abierto |
| Sumario: | Ligand exchange reactions have been used for the synthesis of metallacyclic complexes of Ni and Pd of the type [M[upper bond 1 start](CH2CMe2-o-C6[upper bond 1 end]H4)(P–N)], where P–N is the phosphinito-imine ligand P(iPr)2OC(Me)[double bond, length as m-dash]N(2,6-C6H3(iPr)2. The protic acid [H(OEt2)(BAr′4)] (Ar′ = 3,5-C6H3(CF3)2) selectively cleaves one of the two σ metal–carbon bonds, affording cationic monoalkyl complexes. Nickel monoalkyls stabilized with Et2O or MeCN ligands are thermally unstable and spontaneously undergo a decomposition process that ultimately leads to the breakdown of the phosphinito-imine ligand. In contrast, cationic alkylpalladium derivatives are thermally very stable, allowing the isolation of a formally unsaturated monoalkyl complex stabilized by an intramolecular π-arene interaction. Although monoalkynickel and -palladium phosphinito-imine derivatives are inactive as ethylene polymerization or copolymerization catalysts, they readily experience migratory insertion reactions. A palladium chelate arising from the successive insertion of CO and ethylene has been isolated and characterized. |
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