DFT study of the epoxide ring opening step of the ring opening copolymerisation of epoxide and cyclic anhydride catalyzed by a heterodinuclear Al(III)/K(I) complex

Data to support article: Catalytic Synergy Using Al(III) and Group 1 Metals to Accelerate Epoxide and Anhydride Ring-Opening CopolymerizationsJournal: ACS Catalysis, 2021, DOI:10.1021/acscatal.1c04020https://doi.org/10.1021/acscatal.1c04020 Authors: Wilf Diment,a Georgina L. Gregory,a Andreas Phanopoulos,a Antoine Buchardb and Charlotte K. Williamsa* aChemistry Research Laboratory, Oxford Chemistry, 12 Mansfield Road, Oxford, OX1 3TA, UK. bDepartment of Chemistry, Centre for Sustainable and Circular Technologies, University of Bath, Claverton Down, Bath BA2 7AY, UK *Email: [e-mail] For DFT inquiries: [e-mail] Description: DFT optimised geometries and computed free enthalpies of local minima (intermediates) and local maxima (transition states; validated further by IRC calculations) were used to investigate the mechanism of the reaction between a molecule of cyclohexene oxide and a macrocyclic heterodinuclear Al(III)/K(I) complex (monomer model; with acetate co-ligands), to account for the epoxide ring opening step of the ROCOP process.Protocols:Gaussian16 (rev D.02) softwareFunctional: rwB97XDSolvent model: cpcm=(tetrahydrofuran,read); eps=16; epsinf=1.867Temperature:298.15 KConcentration: 1 mol/LBasis sets:C H: 6-31+g(d,p)K Al O N: 6-311+g(d)Free enthalpies were recomputed using Grimme quasi-harmonic approximation of Grimme, with a cut off frequency of 50 cm–1, and a temperature and concentration correction (T=373.15 K, [CHO]=9.88 mol/L).Content:- Gaussian16 rev A.03 output files - Epoxide ring opening.pdf, illustrating the calculations made and summarising the free enthalpies computed