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The reaction of 2‐[bis(2‐methoxy‐phenyl)phosphanyl]‐4‐methyl‐benzenesulfonic acid (a) and 2‐[bis(2′,6′‐dimethoxybiphenyl‐2‐yl)phosphanyl]benzenesulfonic acid (b) with dimethyl(N,N,N′,N′‐tetramethylethylenediamine)‐palladium(II) (PdMe₂(TMEDA)) leads to the formation of TMEDA bridged palladium based polymerization catalysts (1a and 1b). Upon reaction with pyridine, two mononuclear catalysts are formed (2a and 2b). These catalysts are able to homopolymerize ethylene and also copolymerize ethylene with acrylates or with norbornenes. With ligand b, high molecular weight polymers are formed in high yields, but higher comonomer incorporations are obtained with ligand a.