title: Role(s) of TMA in polymerization.
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.
authors: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy. christian.ehm@unina.it ce.christian.ehm@gmail.com.
authors: C
authors: C
authors: Ehm
authors: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy. christian.ehm@unina.it ce.christian.ehm@gmail.com.
authors: R
authors: R
authors: Cipullo
authors: Department of Chemistry, University of Manitoba, Winnipeg, MB R3T 2N2, Canada.
authors: P H M
authors: PH
authors: Budzelaar
authors: Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Via Cintia, 80126 Napoli, Italy. christian.ehm@unina.it ce.christian.ehm@gmail.com.
authors: V
authors: V
authors: Busico