Mechanism of Carbon Dioxide and Propylene Oxide Ring Opening Copolymerization using a Co(III)/K(I) Heterodinuclear Catalyst

Data to support article: Insights into the Mechanism of Carbon Dioxide and Propylene Ox-ide Ring Opening Copolymerization using a Co(III)/K(I) Heterodinuclear Catalyst Journal of the American Chemical Society DOI:10.1021/jacs.2c06921 https://doi.org/10.1021/jacs.2c06921 Authors: Arron C. Deacy,a Andreas Phanopoulos,a Wouter LIndeboom,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) were used to investigate the mechanism of the alternating copolymerization reaction between molecules of propylene oxide and CO2, catalyzed by a macrocyclic heterodinuclear Co(III)/K(I) complex. Protocols: Gaussian16 (rev C.01) software Functional: rwB97XD Solvent model: cpcm=(tetrahydrofuran,read); eps=16; epsinf=1.867 Basis sets: C H: 6-31+g(d,p) K O N: 6-311+g(d) Co: SDD ECP and basis set Free enthalpies were later recomputed using Grimme quasi-harmonic approximation of Grimme, with a cut off frequency of 100 cm–1, and a temperature and concentration correction (T=323.15 K, [CHO]=9.88 mol/L). On various structures, QTAIM analysis was conducted using the AIMAll package. Non-covalent interactions were analysed using the NCIPLOT 3.0 program Content: - Gaussian16 rev C.02 output files - QTAIM (.wfx (input), .sumviz and .g2dviz) and NCI (.cube) output files. - Summary.xyz : a file that contains all geometries computed - DFT Mechanism.pdf, illustrating the calculations made and summarising the free enthalpies computed