title: Theoretical investigation of the mechanism of cis-trans regulation for the allylnickel(II)-catalyzed 1,4 polymerization of butadiene.
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.
authors.affiliation: Institut für Anorganische Chemie der Martin-Luther-Universität Halle-Wittenberg, Fachbereich Chemie, Kurt-Mothes-Strasse 2, D-06120 Halle, Germany. tobisch@chemie.uni-halle.de
authors.forename: Sven
authors.initials: S
authors.lastname: Tobisch