Extended Data Fig. 1: Computational investigation into the intramolecular acidolysis of the key proposed phenyl potassium intermediate (Int4). | Nature Catalysis

Extended Data Fig. 1: Computational investigation into the intramolecular acidolysis of the key proposed phenyl potassium intermediate (Int4).

From: Identifying palladium culprits in amine catalysis

Extended Data Fig. 1

Relaxed PES scan of proton (highlighted) migration to K-Ph from adjacent B-O-H group showing facile cluster rearrangement to Int4-R followed by proton transfer (via H-trans) to give the acidolysed product Int4-dp. Attempts to model the transition state associated with proton transfer were unsuccessful, which is unsurprising considering the almost flat PES landscape in the region of H-trans. The calculations were performed using Orca 4.2 at the B3LYP-D3BJ/def2-svp level of theory (see Computational Studies section, Supporting Methods for full details); E(elec) of Int4 set to same value as calculated for the ΔG in the literature for comparison purpose; amine group represented as simple tubes, the rest of the cluster as ball-and-stick.

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