Issue 29, 2022

Thermodynamics of metallocene catalyst activation: alignment of theory and experiment

Abstract

Three equilibria involved in metallocene catalyst activation, including dissociation of R6Al2 (R = Me, Et or i-Bu) and related species such as [L2ZrMe2AlMe2][B(C6F5)4] (L2 = Cp2, 1,2-ethylenebis(η5-indenyl), Me2C(η5-C5H4)2) or [(L2ZrMe)2μ-Me][MePBB] (L2 = (h5-1,2-Me2C5H3)2, [MePBB] = [MeB(ArF)3] with ArF = o-C6F5-C6F4) are studied by DFT using various approaches to account for the enthalpy and entropy changes in gas and condensed phases. These studies reveal that both low energy vibrations and translational entropy conspire to cause significant deviations between theory and experiment when it comes to the free energy change in condensed or even gas phase. Alignment of theory with experiment requires in addition, consideration of specific solvation of reactants and products.

Graphical abstract: Thermodynamics of metallocene catalyst activation: alignment of theory and experiment

Supplementary files

Article information

Article type
Paper
Submitted
01 6 2022
Accepted
04 7 2022
First published
05 7 2022
This article is Open Access
Creative Commons BY license

Dalton Trans., 2022,51, 11152-11162

Thermodynamics of metallocene catalyst activation: alignment of theory and experiment

M. Linnolahti and S. Collins, Dalton Trans., 2022, 51, 11152 DOI: 10.1039/D2DT01711C

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements