A series of new pyridinyliminophosphorane bidentate ligands with different steric environments [(2‐C6H4N)PPh2=NAr (NPN)] and their methylpalladium complexes [PdClMe(NPN)] were prepared. From the crystal structure analysis it is evident that the alkyl ligands are always trans to the pyridinyl nitrogen donor, revealing a σ‐donating ability of the iminophosphorane. However, the two Pd−Cl bonds in [PdCl2(NPN)] are essentially the same length. Cationic palladium complexes catalyzed the copolymerization of norbornene/ethylene as well as CO/norbornene. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)
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