Structure-activity relationship of palladium phosphanesulfonates: toward highly active palladium-based polymerization catalysts.

Palladium phosphanesulfonate [R(2)P(C(6)H(4)-o-SO(3))PdMeL] catalysts permit the copolymerization of an exceptional large number of functional olefins with ethylene. However, these catalysts usually have reduced activity. We here have conducted a systematic study on the influence of the phosphane substituent, R, on activity and molecular weight. Phosphanes with strong σ-donating character are shown to lead to the most active catalysts. Thus, the catalyst based on phosphane bis-tert-butyl-phosphanyl-benzenesulfonic acid (R=tBu) exhibits unprecedented high activity, rapidly polymerizing ethylene at room temperature to yield a linear polymer of high molecular weight (M(w)=116,000 g mol(-1)). The influence of the R group on the catalyst ability to incorporate methyl acrylate is also investigated.