Quantifying the Influences of Epoxide Binding in Epoxide/CO2 Ring Opening Copolymerization Catalysis: Computational Chemistry Data

Data to support article:Quantifying the Influences of Epoxide Binding in Epoxide/CO2 Ring Opening Copolymerization CatalysisJournal: Journal of the American Chemical Society (2026)DOI: 10.1021/jacs.5c09088Authors: Katharina H.S. Eisenhardt,a Francesca Fiorentini,a Jae Elise L. Payong, b Ute L. Petri, b Antoine Buchard,c Jenny Yang,b* Charlotte K. Williamsa*aDepartment of Chemistry, Chemistry Research Laboratory, University of Oxford, Oxford OX1 3TA, UKbDepartment of Chemistry, University of California, Irvine, Irvine, California 92697, USAc Department of Chemistry, University of York, Heslington, York YO10 5DD, UKE-mail : [e-mail]: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 various epoxide and CO2, catalyzed by a macrocyclic heterodinuclear Co(III)/K(I) complexProtocol:Gaussian16 (rev C.01) softwareFunctional: rwB97XDSolvent model: cpcm=(tetrahydrofuran,read); eps=16; epsinf=1.867Basis sets:C H: 6-31+g(d,p)K O N: 6-311+g(d)Co: SDD ECP and basis setQuasi-harmonic Gibbs free energies using Cramer and Truhlar’s quasi-harmonic treatment of entropy and Head-Gordon treatment of enthalpy were extracted using the GoodVibes Python library from the optimised structure files. To account for experimental conditions, a temperature of 323.15 K and concentration values as given experimentally were also applied for each system.Conformational searches were performed with CREST v3.0.217, using the GFN2-xTB18 method in the gas phase on the structures of Table S6. For epoxide ring-opening transition states, constraints were applied to the TS bond forming and breaking distances. All other settings were left at their defaults (energy window 6 kcal mol–1; RMSD threshold of 0.125 Å). DFT geometry optimisations of the resulting conformers and quasi-harmonic Gibbs free energies computations were then performed following the procedure outlined above.Content:- Gaussian16 rev C.01 output files- CREST output and ensemble files- Conformational search summary.xlsx, summarising the results of the conformational searches- DFT Mechanism.pdf, illustrating the calculations made and summarising the free enthalpies computed.