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Square planar arenido-(triphenylphosphane)nickel(II) complexes (3) containing a N,O-chelate ligand are catalysts for the carbon monoxide/ethene copolymerisation reaction. Pathways for catalyst deactivation have been elucidated by investigating the reactions of such complexes with aliphatic unsaturated compounds like olefins and alkynes. We have shown that the double or triple bond, respectively, inserts into the nickel-carbon bond followed by β-hydride elimination resulting in aryl-substituted olefins and allenes, which

Polyketones are synthesised by a transition‐metal‐catalysed copolymerisation of olefins and carbon monoxide. Nickel complexes with N,O‐chelating ligands turned out to be promising catalysts in that field. In this work a series of new N,O ligands with an electronically delocalised β‐enaminone backbone were synthesised and fully characterised. The ligand design was inspired by the ligand found in the most efficient nickel catalyst for polyketone synthesis and developed to a highly modular LEGO®‐like arsenal of reactions to versatile substituted β‐enaminone ligands. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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