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Polymerization of arylallenes catalyzed by organo‐rhodium(I) and ‐cobalt (I) complexes to give structurally regulated high‐mass polymers
Author(s) -
Choi J.C.,
Osakada K.,
Yamaguchi I.,
Yamamoto T.
Publication year - 1997
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/(sici)1099-0739(199712)11:12<957::aid-aoc654>3.0.co;2-1
Subject(s) - chemistry , polymerization , rhodium , polymer chemistry , monomer , polymer , catalysis , acetone , trifluoromethyl , cobalt , organic chemistry , alkyl
Organorhodium complexes, such as RhH(PPh 3 ) 4 , RhH(CO)(PPh 3 ) 3 , Rh(η 3 ‐C 3 H 4 Ph)(CO)(PPh 3 ) 2 , and RhH(dppe) 2 [dppe = 1,2‐bis(diphenylphosphinoethane)], catalyze polymerization of phenylallene and of 4‐methylphenylallene at 60 °C. High‐molecular‐weight polymers ( M n >4×10 5 ) are isolated from the reaction products by removing the low‐molecular‐weight ( M n <3×10 3 ) acetone‐soluble fraction. The NMR ( 1 H and 13 C{ 1 H}) spectra of poly(phenylallene) (1) and poly(4‐methylphenylallene) (2) show the structure formed through selective 2,3‐polymerization of the monomers, while similarly obtained poly(2‐naphthylallene) (3) is characterized only by 1 H NMR spectroscopy due to its low solubility in common organic solvents. 4‐Fluorophenylallene and 4‐(trifluoromethyl)‐phenylallene do not polymerize under similar conditions in the presence of RhH(PPh 3 ) 4 catalyst but are turned into low‐molecular‐weight oligomers. CoH(N 2 )(PPh 3 ) 3 ‐catalyzed polymerization of phenylallene and 4‐methylphenylallene at room temperature gives the corresponding polymers with molecular weights in the range M n =(9–15)×10 4 , in high yields. © 1997 John Wiley & Sons, Ltd.