ISSN:
0268-2605
Keywords:
rhodium
;
cobalt
;
polymerization
;
allene
;
hydrido complex
;
Chemistry
;
Industrial Chemistry and Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Organorhodium complexes, such as RhH(PPh3)4, RhH(CO)(PPh3)3, Rh(η3-C3H4Ph)(CO)(PPh3)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 (Mn〉4×105) are isolated from the reaction products by removing the low-molecular-weight (Mn〈3×103) acetone-soluble fraction. The NMR (1H and 13C{1H}) 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 1H 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(PPh3)4 catalyst but are turned into low-molecular-weight oligomers. CoH(N2)(PPh3)3-catalyzed polymerization of phenylallene and 4-methylphenylallene at room temperature gives the corresponding polymers with molecular weights in the range Mn=(9-15)×104, in high yields. © 1997 John Wiley & Sons, Ltd.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
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