Issue 48, 2012

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

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

Supplementary files

Article information

Article type
Paper
Submitted
21 Jun 2012
Accepted
03 Aug 2012
First published
06 Aug 2012

Dalton Trans., 2012,41, 14524-14539

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

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