Role(s) of TMA in polymerization

C. Ehm; R. Cipullo; P. H. M. Budzelaar; V. Busico

doi:10.1039/C5DT04895H

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Role(s) of TMA in polymerization†

C. Ehm,*^a R. Cipullo,^a P. H. M. Budzelaar^b and V. Busico^a

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^a Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy
E-mail: christian.ehm@unina.it, ce.christian.ehm@gmail.com

^b Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada

Abstract

Quenched-flow data for propene polymerization with rac-Me₂Si(2-Me-4-Ph-1-indenyl)₂ZrCl₂/MAO support a picture where removal of MAO qualitatively changes the kinetic profile from a mainly enthalpic to a mainly entropic barrier. DFT studies suggest that a not previously recognized singly-bridged end-on coordination mode of Me₆Al₂ to catalytically active centers may be kinetically relevant as a resting state. In contrast, the more traditional doubly-bridged complex of Me₃Al is proposed to be more relevant to chain transfer to cocatalyst.

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DOI: https://doi.org/10.1039/C5DT04895H
Article type: Paper
Submitted: 15 Dec 2015
Accepted: 28 Jan 2016
First published: 29 Jan 2016

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Dalton Trans., 2016,45, 6847-6855

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Role(s) of TMA in polymerization

C. Ehm, R. Cipullo, P. H. M. Budzelaar and V. Busico, Dalton Trans., 2016, 45, 6847 DOI: 10.1039/C5DT04895H

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Dalton Transactions

Role(s) of TMA in polymerization†

Abstract

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Role(s) of TMA in polymerization

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