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Model studies of Ziegler-Natta olefin polymerization using group 3 and group 4 metallocenes

Citation

Yoder, Jeffrey Charles (2001) Model studies of Ziegler-Natta olefin polymerization using group 3 and group 4 metallocenes. Dissertation (Ph.D.), California Institute of Technology. https://resolver.caltech.edu/CaltechTHESIS:04072014-140228693

Abstract

Evidence for the stereochemical isomerization of a variety of ansa metallocene compounds is presented. For the scandocene allyl derivatives described here, we have established that the process is promoted by a variety of salts in both ether and hydrocarbon solvents and is not accelerated by light. A plausible mechanism based on an earlier proposal by Marks, et al., is offered as an explanation of this process. It involves coordination of anions and/or donor solvents to the metal center with cation assistance to encourage metalcyclopentadienyl bond heterolysis, rotation about the Si-Cp bond of the detached cyclopentadienide and recoordination of the opposite face. Our observations in some cases of thermodynamic racemic:meso ratios under the reaction conditions commonly used for the synthesis of the metallocene chlorides suggests that the interchange is faster than metallation, such that the composition of the reaction mixture is determined by thermodynamic, not kinetic, control in these cases.

Two new ansa-scandocene alkenyl compounds react with olefins resulting in the formation of η3-allyl complexes. Kinetics and labeling experiments indicate a tuck-in intermediate on the reaction pathway; in this intermediate the metal is bound to the carbon adjacent to the silyllinker in the rear of the metallocene wedge. In contrast, reaction of permethylscandocene alkenyl compounds with olefins results, almost exclusively, in vinylic C-H bond activation. It is proposed that relieving transition state steric interactions between the cyclopentadienyl rings and the olefin by either linking the rings together or using a larger lanthanide metal may allow for olefin coordination, stabilizing the transition state for allylic σ-bond metathesis.

A selectively isotopically labeled propylene, CH2CD(13CH3), was synthesized and its polymerization was carried out at low concentration in toluene solution using isospecific metallocene catalysts. Analysis of the NMR spectra (13C, 1H, and 2H) of the resultant polymers revealed that the production of stereoerrors through chain epimerization proceeds exclusively by the tertiaryalkyl mechanism. Additionally, enantiofacial inversion of the terminally unsaturated polymer chain occurs by a non-dissociative process. The implications of these results on the mechanism of olefin polymerization with these catalysts is discussed.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Bercaw, John E.
Thesis Committee:
  • Unknown, Unknown
Defense Date:8 June 2000
Record Number:CaltechTHESIS:04072014-140228693
Persistent URL:https://resolver.caltech.edu/CaltechTHESIS:04072014-140228693
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8181
Collection:CaltechTHESIS
Deposited By: Benjamin Perez
Deposited On:07 Apr 2014 21:27
Last Modified:02 Dec 2020 02:51

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