Orders in Catalyst and Catalyst Deac;va;on: Using the opQmised workflow, the orders in catalyst and reagent were invesQgated. VariaQon of the concentraQon of [Pd(PAd2 n Bu)2] across a 1.7 mM to 4.6 mM concentraQon range was invesQgated for the formylaQon of 0.8 M soluQons of 4-bromoanisole in toluene at 100 °C, 5 bar of 1:1 CO:H2 and 0.75 equiv. TMEDA. No inducQon period is observed in the kineQc profiles. The lack of an inducQon period suggests that [Pd(PAd2 n Bu)2] is either an on-cycle species or undergoes a fast event, such as ligand dissociaQon, to generate an on-cycle species. VTNA shows a clear fit to 1 st order behavior in catalyst (Fig. ). The kineQc profiling was repeated with 4bromobenzotrifluoride, data again fit 1 st order in catalyst. Using RPKA, a same excess experiment with 4-bromoanisole was conducted to explore the possibility of catalyst deacQvaQon. Time-shived kineQc profiles show good overlap with the standard condiQons, suggesQng that catalyst deacQvaQon is not significant under the condiQons of the OSR kineQc runs (Fig. ).