The reaction between the palladate salt and a prototypical hindered monodentate ligand was initially examined by multinuclear NMR to assess the ease with which bromide can be displaced from palladium (Figure ). Upon mixing PAd3 and 2 (1:1 P/Pd) in CD2Cl2 for 10 min at RT, consumption of free phosphine was observed by 31 P NMR with concomitant formation of a single new species (δP 41.9 ppm) matching the reported chemical shift of (PAd3)Pd(4-C6H4F)Br (1). 9b Complex 2, which exists as a mixture of monomer (minor) and syn/anti diastereomers (major), was fully consumed based on the 19 F NMR spectrum of the solution. A single new species was observed (δF -122.8 ppm) also matching literature data for the T-shaped complex 1. These data confirm the capacity for the palladate salt to undergo phosphine for bromide ligand substitution within minutes at ambient temperature and catalytically relevant concentration. Reaction of palladate 2 with a series of other mono-and bisphosphines was next investigated to test the generality of OAC formation (Scheme 1). Yields were determined by F NMR spectroscopy using 1,4-difluorobenzene as internal standard. In addition to the high yield of 1 (86%), reaction of the palladate with 2 equiv of PPh3 (vs.