Effect of ligand structure in the trimethylene carbonate polymerization by cationic zirconocene catalysts: A “naked model” DFT study

Coordination Ring-Opening Polymerization of Cyclic Esters: A Critical Overview of DFT Modeling and Visualization of the Reaction Mechanisms

“…Cationic coordination polymerization of TMC catalyzed by different zirconocenes was studied in silico by Jitonnom and Meelua [113,114] using DFT calculations at the B3LYP/6-31G(d)-LANL2DZ [51,53,54,78] level of theory. The reaction mechanism was similar to the mechanism presented in Figure 15.…”

DFT study of formation and properties of dinuclear zirconocene cations: Effects of ligand structure, solvent, and metal on the dimerization process

“…3), 38 dinuclear zirconocene structures were built and optimized using the initial coordinates reported in the literature [15]. The choices of the catalysts were based on our recent study on the trimethylene carbonate polymerization [14]. In brief, 20 ligands were based on available X-ray crystallographic structures (denoted as Cn) and 18 ligands were computationally modeled here (denoted as Hn) for comparison purposes.…”

“…Recently, a number of experimental studies have been conducted to characterize and/or improve the CROP activity by introducing ligand framework modification to the catalyst structure in combination of different catalytic systems [7,12]. We have recently utilized density functional theory (DFT) calculations to probe the effects of ligand structure [13][14][15] and the ring size [6] on the activity of zirconocene-catalyzed CROP, providing atomistic description of all cationic species of the process. These studies focus on the role of ligand structure on the CROP using group 4 metallocene/coctalyst as a catalytic system, which involve the [Cp2MR] + compound.…”

Data on electronic structures for the study of ligand effects on the zirconocene-mediated trimethylene carbonate polymerization

“…isolated cation ( Cation ) TMC-activated complex ( Complex ) reactant ( Re ) transition state ( TS ) and product ( Pr ) (see Ref. [1] for more details) in the initiation and first propagation step of cationic ring-opening polymerization (CROP). The dataset of 29 catalyst structures were generated from density functional theory (DFT) calculations [2] , [3] , [4] .…”

“… The data presented in this paper are related to the research article entitled “Effect of ligand structure in the trimethylene carbonate polymerization by cationic zirconocene catalysts: A “naked model” DFT study” (Jitonnom and Meelua, 2017) [1] . In this data article, we present 3D molecular information of 29 zirconocene catalysts that differ in electronic and steric properties.…”