Heterocycle-Substituted Phosphinesulfonato Palladium(II) Complexes for Insertion Copolymerization of Methyl Acrylate

A family of heterocycle-substituted binuclear phosphinesulfonato Pd(II) complexes {[R2P(C6H4SO2O)]PdMeClLi(dmso)}2 (1a–d-LiCl-dmso: 1a-LiCl-dmso, R = 2-furyl; 1b-LiCl-dmso, R = 2-thienyl; 1c-LiCl-dmso, R = 2-(N-methyl)pyrrolyl; 1d-LiCl-dmso, R = 2-benzofuryl) was synthesized, and the solid-state structures of 1a–c-LiCl-dmso were determined, which revealed various modes of bridging between the two metal fragments. 1a–d-LiCl-dmso further generated either the mononuclear Pd(II) complexes {[κ2P,O-R2P(C6H4SO2O)]PdMe(pyr)} (1a–d-pyr) by addition of pyridine or the more labile mononuclear Pd(II) complex {[κ2P,O-(2-thienyl)2P(C6H4SO2O)]PdMe(dmso)} (1b-dmso) by chloride abstraction with AgBF4. Stoichiometric methyl acrylate (MA) insertion experiments indicated that, in comparison with the other three substituents, the thienyl-substituted Pd(II) complexes undergo faster insertion of MA in a primary 2,1-fashion, and 1b-dmso possesses the fastest insertion rate due to the relative weakly coordinating dmso molecule. A...

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