Mechanism of the chain termination of the allylnickel(II)-catalyzed polymerization of 1,3-butadiene. A density functional investigation for the cationic [NiII(RC3H4)(cis-C4H 6)L]+ active catalyst

Macromolecules

Volumn 36, Issue 16, 2003, Pages 6235-6244

  Tobisch, Sven ^a  

^a MARTIN LUTHER UNIVERSITY HALLE WITTENBERG   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN TRANSFER MECHANISM;

MONOMERS; POLYMERIZATION; PROBABILITY DENSITY FUNCTION; STEREOCHEMISTRY;

CATALYSTS;

EID: 0042475492     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma034369v     Document Type: Article

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87. 19
88. 4-units. This catalyst model allowed a reliable description of elementary processes that are either facilitated (allylic isomerization) or not (monomer insertion, chain termination) by the coordination of the first double bond of the polybutadienyl chain to nickel.
89. (b) The barriers of individual elementary steps are given relative to the corresponding precursor species.
90. he) are displayed by dashed lines.
91. 13 polybutadienyl chain is displayed in a shrunken fashion, to simplify the drawing.
92. Please note, that the energetics for the 1 ⇌ 2 substitution equilibrium (cf. Scheme 3a) has to be taken into account as well in order to make the reported results compatible with experimentally derived kinetic data, since 1s is prevalent.