Journal of Structural Chemistry

, Volume 41, Issue 2, pp 318–328 | Cite as

Quantum chemical models and electronic structure of active centers of heterogeneous polymerization of olefins

  • I. I. Zakharov


The peculiarities of the catalytic activity in olefin polymerizations which can find explanation in terms of the concepts suggested in this work are as follows.

First, the low catalytic activity of the individual organometal compounds of group IV-VI transition metals is indicative [53] of the important role of the coordination state of the transition metal in AC, which, according to Cosse's model, must be octahedral (tetrahedral for individual metal-alkyl compounds MRn).

Second, the activity of a catalytic system depends essentially on the nature of the ligand environment of the metal in AC. The catalysts based on titanium halides display the highest activity.

Third, the results of [19, 20] show that the highly active catalytic centers of homogeneous Ziegler-Natta's systems are “cation-like” Zr(IV) complexes Cp2Zr+-R. All these features find explanation in terms of the concept of the competitive contributions from the AC metal s and d orbitals to the active M-R bond. Thus a transition of AC environment from tetrahedral to octahedral may be compared with a change in transition metal AO hybridization:d 3s1 (tetrahedron) ⇒d 3s1 (octahedron).


Chain Propagation Orbital Structure Insertion Reaction Hydride Transfer Orbital Contribution 


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Copyright information

© Kluwer Academic/Plenum Publishers 2000

Authors and Affiliations

  • I. I. Zakharov
    • 1
  1. 1.Institute of Catalysis, Siberian BranchRussian Academy of SciencesUSSR

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