Abstract: The present paper gives a brief review of quantum-chemical studies of the electronic structure of the active centers (AC) and mechanism of the growth reaction in the catalytic polymerization of alkenes. The first part gives general information on the electronic approximations (the CNDO, Wolfsberg-Helmholz-Ballhausen, and Slater-Johnson methods) used for the analysis of electronic aspects of catalytic polymerization. The second section summarizes the chief experimental data on the composition of the AC and the mechanism of the growth reaction (chiefly for Ziegler-Natta catalysts). The third section gives an analysis of the electronic structure of the AC, dealing with the mutual influence of the metal-alkene and metal-alkyl bonds. The metal-alkene bond is chiefly donor-acceptor in character; the influence of dative interaction is slight. Electron transition between the alkyl ~ orbital and the metal d orbital cannot determine the principle of the catalytic action of the transition metal ion in the polymerization reaction, as suggested by Cossee and coworkers. The last section includes a quantum-chemical analysis of the stages involving the coordination of the alkene and the insertion of the coordinated monomer at the metal-carbon bond. It is concluded that the growth reaction takes place preferentially by a two-stage mechanism. The insertion stage requires little activation energy and is accompanied by the formation of the stable cis configuration of the alkyl. The limiting stage is apparently the stage involving the coordination of the alkene, for which the nature of the activation energy is related to the rearrangement of the growing end of the polymer chain under the influence of the coordinated monomer.

Cite: Avdeev V.I. , Zakharov I.I. , Zakharov V.A. , Bukatov G.D. , Ermakov Y.I.
Quantum-Chemical Study of the Mechanism of the Growth Reaction in the Catalytic Polymerization of Alkenes
Journal of Structural Chemistry. 1977. V.18. N3. P.420-436. DOI: 10.1007/BF00753089 WOS Scopus РИНЦ OpenAlex

Original: Авдеев В.И. , Захаров И.И. , Захаров В.А. , Букатов Г.Д. , Ермаков Ю.И.
Квантово-химическое исследование механизма реакции роста при каталитической полимеризации олефинов
Журнал структурной химии. 1977. Т.18. №3. С.525-545. РИНЦ ANCAN

Dates:

Submitted:	Jan 20, 1977
Published print:	May 1, 1977

Identifiers:

Web of science:	WOS:A1977EM27800007
Scopus:	2-s2.0-34250280855
Elibrary:	31366069
OpenAlex:	W2030659914

Citing:

DB	Citing
Web of science	1
Scopus	1
OpenAlex	2

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