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Living polymerization of phenylacetylene by rhodium‐based ternary catalysts, (diene)Rh(I) complex/vinyllithium/phosphorus ligand. Effects of catalyst components
Author(s) -
Misumi Yoshihiko,
Kanki Keiji,
Miyake Michihiro,
Masuda Toshio
Publication year - 2000
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/1521-3935(20001101)201:17<2239::aid-macp2239>3.0.co;2-p
Subject(s) - phenylacetylene , chemistry , polymerization , substituent , rhodium , polymer chemistry , diene , triphenylphosphine , living polymerization , catalysis , ligand (biochemistry) , medicinal chemistry , organic chemistry , radical polymerization , polymer , natural rubber , biochemistry , receptor
It was proved that a Rh‐based ternary catalyst composed of [(nbd)RhCl] 2 (nbd: bicyclo[2.2.1]hepta‐2,5‐diene), (triphenylvinyl)lithium, and triphenylphosphine induces living polymerization of phenylacetylene. [(nbd)RhCl] 2 was effective as the main catalyst, whereas neither [(cod)RhCl] 2 (cod: 1,5‐cyclooctadiene) nor [(coe) 2 RhCl] 2 (coe: cyclooctene) induced living polymerization. The anionic ligands such as chlorine, methoxy, and acetoxy groups in the Rh complex hardly affected the living polymerization. When vinyllithium as second catalyst component possessed a bulky substituent such as phenyl or t ‐butyl group on its α ‐carbon, stable vinylrhodium species were generated, which led to living polymerization. At least one substituent was necessary on the β ‐carbon of the vinyllithium for the living polymerization. Tris(4‐substituted phenyl)phosphines worked well as third components among various phosphorus ligands. The polymerization was decelerated as the basicity of the phosphine ligand increased.