Metallacyclic mechanism of the addition polymerization of norbornene involving Ni(I) and Ni(III) complexes

The catalytic system Ni(COD) 2 /BF 3 ·OEt 2 is highly active in the addition polymerization of nor-bornene (NB). Its activity, which is up to 1930 (kg NB) (mol Ni) −1 h −1 , is higher than the activity of the other known nickel complex catalysts. Another advantage of this system over the latter is t...

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Bibliographic Details
Published in:Kinetics and catalysis 2012-07, Vol.53 (4), p.456-461
Main Authors: Saraev, V. V., Kraikivskii, P. B., Bocharova, V. V., Matveev, D. A.
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
Chemistry and Materials Science
Physical Chemistry
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Summary:The catalytic system Ni(COD) 2 /BF 3 ·OEt 2 is highly active in the addition polymerization of nor-bornene (NB). Its activity, which is up to 1930 (kg NB) (mol Ni) −1 h −1 , is higher than the activity of the other known nickel complex catalysts. Another advantage of this system over the latter is that it contains a smaller proportion of a Lewis acid (5 molar parts or below) and no conventional stabilizing organoelement ligands. The activity of this system in NB polymerization has been investigated by Fourier-transform IR spectroscopy. According to EPR data, NB polymerization is accompanied by the formation of low-spin complexes of trivalent nickel, which result from the oxidative addition of the monomer to univalent nickel complexes. A metallacyclic mechanism involving Ni(I) and Ni(III) complexes is suggested for NB polymerization.
ISSN:0023-1584
1608-3210
DOI:10.1134/S002315841204009X