Polymerization of arylallenes catalyzed by organo-rhodium(I) and -cobalt (I) complexes to give structurally regulated high-mass polymers
✍ Scribed by J.-C. Choi; K. Osakada; I. Yamaguchi; T. Yamamoto
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 143 KB
- Volume
- 11
- Category
- Article
- ISSN
- 0268-2605
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✦ Synopsis
Organorhodium
complexes, such as RhH(PPh 3 ) 4 , RhH(CO)(PPh 3 ) 3 , Rh( 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 > 4ϫ 10 5 ) are isolated from the reaction products by removing the low-molecular-weight (M n < 3ϫ 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-molecularweight 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)ϫ 10 4 , in high yields.