We investigated the path which the reaction sequence A and B takes with DavePhos as ligand (Figure ) computationally using DFT calculations (see SI for details). The oxidative addition step (reaction A) was found as rate determining step with an activation energy (ΔG ‡ ) of 6.9 kcal/mol. In addition, it was found that the amino group on DavePhos mediates the docking of the activated boronic acid to the catalytic system through a hydrogen bond (Figure ). The energy of the transition state TS1 (oxidative addition) was found to be lower for DavePhos than for XPhos by 2.8 kcal/mol. Figure shows also that the formation of this transition state with [B12H11Br] 2-is energetically much less favorable, explaining why only [B12H11I] 2-could be used successfully as substrate for cross-coupling reactions.