43.
Novel triarylamine‐based coordination‐saturated aryl Pd(II) halide complexes ligated by PEt
3, PCy
3, and P(
o‐tol)
3 were successfully synthesized by direct oxidative addition of aryl halide to the corresponding Pd(0) precursors. Suzuki–Miyaura coupling polymerization of 2‐(7‐halide‐9,9‐dioctylfluoren‐2‐yl)?1,3,2‐dioxaborinane with these Pd(II) complexes as initiators was investigated for the synthesis of poly(fluorene)s with triarylamine end group. Pd(II) complexes with PCy
3 or P(
o‐tol)
3 exhibited catalytic activity and realized the catalyst‐transfer polycondensation at 75 °C and room temperature, respectively, while the polymerization using Pd(II) catalyst ligated by PEt
3 did not proceed, which indicated that the bulky phosphine ligands could facilitate the reductive elimination and further promote the polymerization. In addition, the dimeric Pd(II) complex with P(
o‐tol)
3 can convert into monomeric Pd(II) intermediate with an open coordination site, which had a higher activity. The end groups of the afforded polyfluorene were analyzed by matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectrometry, in which the Ar/H end groups are indicative of the catalyst‐transfer polymerization. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 ,
53, 1457–1463
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