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Quantum chemical characteristics of cationic active sites forming in the Bcl 3 ‐α,ω‐dichloroalkyl systems
Author(s) -
Yakimansky Alexander V.,
Erussalimsky Boris L.,
Zubkov Vladimir A.
Publication year - 1994
Publication title -
macromolecular theory and simulations
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.37
H-Index - 56
eISSN - 1521-3919
pISSN - 1022-1344
DOI - 10.1002/mats.1994.040030216
Subject(s) - mndo , cationic polymerization , quantum chemical , chemistry , ion , polymerization , propene , computational chemistry , polymer chemistry , molecule , organic chemistry , catalysis , polymer
Taking as examples the cyclic halonium (I) and linear carbenium (II) model cations of equal composition, viz. [Cl(CH 2 ) 4 ] + , and products of propene addition to them (V and VI), the energetic characteristics of these structures were estimated by the MNDO (a) method. The energetic preference of I with respect to II was found to be much higher than that of V with respect to VI (ca. 97 and ca. 11 kJ/mole, respectively). This difference is suggested to reflect the decrease in the tendency of linear Cl‐containing carbenium ions to cyclization into halonium ions with an increase in the length of the linear hydrocarbon chain. The results obtained are applied to the discussion of the mechanism of polymerization in the 2‐methylpropene‐BCl 3 ‐2,5‐dichloro‐2,5‐dimethylhexane system.