The preparation and reactivity of elusive palladium proazaphosphatrane complexes that represent putative intermediates in C−N cross-coupling reactions are described. Variable transannulation in these compounds, as determined by X-ray crystallography, validates the previously untested hypothesis that proazaphosphatranes undergo conformational changes to stabilize catalytic intermediates. The competence of these complexes as catalytic intermediates is supported through stoichiometric and catalytic coupling reactions, providing the first examples of discrete proazaphosphatrane complexes employed in cross-coupling.