In conclusion, we have shown that a crystalline, air-stable arylpalladate salt [Pd(4-C6H4F)(Br)µ-Br]2•2[NPr4] (2) undergoes ligand substitution of halide for a monophosphine, N-heterocyclic carbene (NHC), or bisphosphine ancillary ligand to form Pd oxidative addition complexes (OACs) in solution. The ligand exchange can occur even at low temperature as exemplified by the synthesis of an unprecedented Pd OAC [(IPr)Pd(4-C6H4F)Br]n (3g) coordinated by a single NHC ligand. At room temperature 3g underwent C-C reductive elimination rationalizing why its synthesis via direct oxidative addition to Pd(0) complexes had remained so elusive. Head-tohead comparisons of on-demand versus isolated Pd OACs or other contemporary Pd precatalysts in a suite of challenging C-C, C-N, and C-O coupling reactions demonstrated competitive performance from a singular palladate precursor. Generation of these species in solution in a modular fashion bypasses the need for independent syntheses of every unique OAC as a prerequisite to exploring applications of these state-of-the-art "on-cycle" catalysts. This approach should be attractive for high throughput experimentation or when complications associated with activation of traditional precatalysts are a concern.