title: Structure-activity relationship of palladium phosphanesulfonates: toward highly active palladium-based polymerization catalysts.
abstract: 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.
authors.affiliation: Quebec Center for Functional Materials-NanoQAM, Department of Chemistry, UQAM, Succ Centre Ville-CP 8888, Montreal, QC, H3C3P8, Canada.
authors.forename: Laurence
authors.initials: L
authors.lastname: Piche
authors.forename: Jean-Christophe
authors.initials: JC
authors.lastname: Daigle
authors.forename: Gregor
authors.initials: G
authors.lastname: Rehse
authors.forename: Jerome P
authors.initials: JP
authors.lastname: Claverie