Notes and references ‡ A full conformational search for each intermediate was carried out using CREST and xTB. Geometry optimisations were carried out (without a solvent model) using the M06-L functional, the SDD basis set/ECP on iridium, and the 6-311G(d,p) basis set on all other atoms. Energies were refined using single point calculations at M06-L/Def2-QZVP with the SMD solvation model (with chloroform or DCM solvent, as appropriate). Quasi-harmonic corrections to entropy and enthalpy were applied using GoodVibes. Further details of the level of theory can be found in the Supporting Information. Methyl benzoate was used as a model for ethyl benzoate to decrease conformational complexity. The BAr F 24 counterion was not modelled, and only the cationic iridium fragment is considered throughout (BAr F 24 = tetrakis(3,5trifluoromethylphenyl)borate. DFT data (coordinates, energies, etc.) can be accessed either via the Supporting Information † or via ioChem-BD (DOI: TBC).