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

Abstract

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. The data contains all cationic species along the initiation and first propagation step of the polymerization, which are provided in a PDB format that can be used for further studies.

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.…”

Mechanism of cationic ring-opening polymerisation of ε-caprolactone using metallocene/borate catalytic systems: a DFT and NCI study on chain initiation, propagation and termination

“…This DFT/mixed basis set method has been widely used for transition metal complexes. [35][36][37][38] Vibrational frequency calculations were carried out to conrm the transition states and local minima obtained and to determine the zero-point vibrational energies (ZPE) and thermal corrections to the enthalpic (H) and Gibbs free energies (G) at standard temperature and pressure (298.15 K and 101.325 kPa). Geometry optimizations were also performed in toluene at the same level as the gas-phase optimised geometries, using the SMD/SCRF method 39 (toluene, 3 = 2.374).…”

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].…”

“…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.…”

“…The electronic structures and thermal stability of the dimers are then determined according to the analyses of geometric and electronic properties of these ligands. DFT methods have been widely applied in many related studies [6,15,27,28] to provide a detailed description for the chemistry of the cationic ROP process. We also considered the catalytic route (Eq.…”