Jump to main content
Jump to site search

Issue 48, 2012
Previous Article Next Article

Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand

Author affiliations

Abstract

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.

Graphical abstract: Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand

Back to tab navigation

Supplementary files

Publication details

The article was received on 21 Jun 2012, accepted on 03 Aug 2012 and first published on 06 Aug 2012


Article type: Paper
DOI: 10.1039/C2DT31334K
Citation: Dalton Trans., 2012,41, 14524-14539
  •   Request permissions

    Migratory insertion reactions of nickel and palladium σ-alkyl complexes with a phosphinito-imine ligand

    L. Ortiz de la Tabla, I. Matas, E. Álvarez, P. Palma and J. Cámpora, Dalton Trans., 2012, 41, 14524
    DOI: 10.1039/C2DT31334K

Search articles by author

Spotlight

Advertisements