This report describes a combined experimental and computational investigation of the mechanism of C(sp(3))-N bond-forming reductive elimination from sulfonamide-ligated Pd-IV complexes. After an initial experimental assessment of reactivity, we used ZStruct, a computational combinatorial reaction finding method, to analyze a large number of multistep mechanisms for this process. This study reveals two facile isomerization pathways connecting the experimentally observed Pd-IV isomers, along with two competing S(N)2 pathways for C(sp(3))-N coupling. One of these pathways involves an unanticipated oxygen nitrogen exchange of the sulfonamide ligand prior to an inner-sphere S(N)2-type reductive elimination. The calculated Delta G(double dagger) values for isomerization and reductive elimination with a series of sulfonamide derivatives are in good agreement with experimental data. Furthermore, the simulations predict relative reaction rates with different sulfonamides, which is successful only after considering competition between the proposed operating mechanisms. Overall, this work shows that the combination of experimental studies and new computational tools can provide fundamental mechanistic insights into complex organometallic reaction pathways.