Theoretical Investigation of the Mechanism of Cis−Trans Regulation for the Allylnickel(II)-Catalyzed 1,4 Polymerization of Butadiene
- 5 January 2002
- journal article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 35 (2), 96-104
- https://doi.org/10.1021/ar010001b
Abstract
In this Account we summarize the recent progress in the computational modeling of the transition-metal-catalyzed 1,3-diene polymerization. We present a comprehensive and theoretically well-founded view of the cis−trans regulation mechanism of the intriguing C−C coupling for the allylnickel(II)-catalyzed 1,4 polymerization of butadiene. The crucial elementary reactions of the entire polymerization process were theoretically explored for typical trans-1,4- and cis-1,4-regulating catalysts. As a result, the catalytic structure−activity relationships are deduced, which are responsible for opening that reaction channel which yields trans-1,4 and cis-1,4 polymer units.Keywords
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