Employing Pd(OAc)(2), a facile deprotonation route to access highly basic tris(alkylimido)phosphate trianions, {(RN)(3)PO](3-) (R = Bu-t, (c)Hex, or Pr-i), analogous to the orthophosphate (PO43-) ion in polar and in protic solvents has been achieved. Trinuclear and prismatic Pd(II) clusters of these imido trianions having the formula {Pd-3[(NR)(3)PO](OAc)(3)}(n) (n = 1 or 2) or as Mixed-bridged clusters of the type {Pd-3[((NPr)-Pr-i)(3)PO](OAc)(2)(OR')}(2) (R' = Me or H) were isolated exclusively in all these reactions in which the trianionic species acts as a tripodal chelating ligand to the trinuclear Pd-3 unit. Reactivity studies aiming at the Pd(II) atoms in these clusters with nucleophilic reagents, such as primary amines (R '' NH2), have led to a new trimetic cluster with the formula {Pd-3[(NR)(3)PO](OAc)(3)(R '' NH2)(3)} in which the tripodal coordination of the Pd-N-imido moieties remained unaffected, exemplifying the robustness of the Pd-3 unit in all these clusters. We have also shown the catalytic activity of these Pd(II) complexes in Mizoroki-Heck type coupling reactions in the presence of Cu(OAc)(2).