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Structure–Activity Relationship of Palladium Phosphanesulfonates: Toward Highly Active Palladium‐Based Polymerization Catalysts
Author(s) -
Piche Laurence,
Daigle JeanChristophe,
Rehse Gregor,
Claverie Jerome P.
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103694
Subject(s) - palladium , catalysis , ethylene , substituent , benzenesulfonic acid , polymerization , methyl acrylate , chemistry , copolymer , polymer chemistry , yield (engineering) , polymer , organic chemistry , materials science , metallurgy
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= t Bu) 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.