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Stable metal‐carbene complexes as initiators for ring‐opening polymerization of cyclo‐olefins
Author(s) -
Doherty Martin,
Siove Alain,
Parlier Andrée,
Rudler Henri,
Fontanille Michel
Publication year - 1986
Publication title -
makromolekulare chemie. macromolecular symposia
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.257
H-Index - 76
eISSN - 1521-3900
pISSN - 0258-0322
DOI - 10.1002/masy.19860060107
Subject(s) - carbene , norbornene , chemistry , polymerization , intramolecular force , polymer chemistry , transition metal carbene complex , metal , photochemistry , stereochemistry , organic chemistry , catalysis , polymer
The use of stable metal‐carbene complexes to initiate the polymerization of norbornene allows to know the exact nature of active centers propagating the polymerization. Complexes showing an intramolecular coordination of a double‐bond on the transition metal atomoffer a satisfactory compromise between stability and activity and are used to study the initiation step. It is shown that the kinetically limiting step of the process is the liberation of a coordination site in cis‐position with respect to the carbene carbon. The effect of several physical and chemical factors on the activity of initiator complex is studied. In particular, the mechanism of activation by Lewis acids is analyzed by 13 C and 1 H NMR on the system complex III/Al(C 2 H 5 ) 3 .