This pathway can be considered to be iniQated from Int-1 a weakly bound van der Waals complex between [Pd(PAd2 n Bu)] and the aryl bromide. Int-1 is likely in equilibrium with Int-2, a conformer in which the n Bu group of the phosphine ligand forms an agosQc interacQon through the g-posiQon of the carbon chain. Spectroscopic characterisaQon of agosQc interacQons in these types of 3-coordinate complexes is common. reacts with aryl bromides at 70 °C. Phosphine dissociaQon likely plays a significant role in determining rate as the same complexes can be accessed at 25 °C from [Pd(dba)2] and 1 equiv. of PAd2 n Bu (dba = dibenzylideneacetone). CompeQQon experiments are also consistent with predicted barriers for oxidaQve addiQon decreasing for more electron-deficient substrates. These predicted electronic effects do not match those observed in the Hammee analysis. Rather oxidaQve addiQon is expected to be an accessible and non-reversible step that precedes the turnover-limiQng sequence.