Effects of pendant ligand binding affinity on chain transfer for 1-hexene polymerization catalyzed by single-site zirconium amine bis-phenolate complexes.

Abstract

The kinetics of 1-hexene polymerization using a family of five zirconium amine bis-phenolate catalysts, Zr[tBu-ON(X)O]Bn2 (where X = THF (1), pyridine (2), NMe2 (3), furan (4), and SMe (5)), has been investigated to uncover the mechanistic effect of varying the pendant ligand X. A model-based approach using a diverse set of data including monomer consumption, evolution of molecular weight, and end-group analysis was employed to determine each of the reaction specific rate constants involved in a given polymerization process. The mechanism of polymerization for 1-5 was similar and the necessary elementary reaction steps included initiation, normal propagation, misinsertion, recovery from misinsertion, and chain transfer. The latter reaction, chain transfer, featured monomer independent β-H elimination in 1-3 and monomer dependent β-H transfer in 4 and 5. Of all the rate constants, those for chain transfer showed the most variation, spanning 2 orders of magnitude (ca. (0.1-10) × 10(-3) s(-1) for vinylidene and (0.5-87) × 10(-4) s(-1) for vinylene). A quantitative structure-activity relationship was uncovered between the logarithm of the chain transfer rate constants and the Zr-X bond distance for catalysts 1-3. However, this trend is broken once the Zr-X bond distance elongates further, as is the case for catalysts 4 and 5, which operate primarily through a different mechanistic pathway. These findings underscore the importance of comprehensive kinetic modeling using a diverse set of multiresponse data, enabling the determination of robust kinetic constants and reaction mechanisms of catalytic olefin polymerization as part of the development of structure-activity relationships.

DOI: 10.1021/ja401474v

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Cite this paper

@article{Steelman2013EffectsOP, title={Effects of pendant ligand binding affinity on chain transfer for 1-hexene polymerization catalyzed by single-site zirconium amine bis-phenolate complexes.}, author={D Keith Steelman and Silei Xiong and Paul D Pletcher and Erin F Smith and Jeffrey M Switzer and Grigori A. Medvedev and W. Nicholas Delgass and James M. Caruthers and Mahdi M Abu-Omar}, journal={Journal of the American Chemical Society}, year={2013}, volume={135 16}, pages={6280-8} }