Quenched-flow data for propene polymerization with rac-Me2Si(2-Me-4-Ph-1-indenyl)(2)ZrCl2/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.
Role(s) of TMA in polymerization / Ehm, Christian; Cipullo, Roberta; Busico, Vincenzo; Budzelaar, Peter H. M.. - In: DALTON TRANSACTIONS. - ISSN 1477-9226. - 45:16(2016), pp. 6847-6855. [10.1039/c5dt04895h]
Role(s) of TMA in polymerization
Ehm, Christian;CIPULLO, ROBERTA;BUSICO, VINCENZO;
2016
Abstract
Quenched-flow data for propene polymerization with rac-Me2Si(2-Me-4-Ph-1-indenyl)(2)ZrCl2/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.File | Dimensione | Formato | |
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