Bis(diphosphanylamido) complexes of strontium and europium, [{(Ph2P)(2)N}(2)M(THF)(3)] (M = Sr (1), Eu (2)), have been prepared by reaction of [K(THF)(n)][N(PPh2)(2)] (n = 1.25, 1.5) and MI2. The single-crystal X-ray structures of compounds 1 and 2 always show a eta(2) coordination of the ligand via the nitrogen and one phosphorus atom. In solution, a dynamic behavior of the ligand is observed, which is caused by the rapid exchange of the two different phosphorus atoms. As a result of the radius of the larger ion, treatment of [K(THF)n][N(PPh2)(2)] with BaI2 gives the coordination polymer [{(Ph2P)(2)N}(2)Ba(THF){(Ph2P)(2)N}K], (3). Two of the three {(Ph2P)(2)N}(-) ligands of compound 3 bind to the metal in n(2) (N, P) while the third shows a heteroallylic (P, P) coordination mode. In the solid state, the infinite chain is formally held together by pi coordination of the phenyl rings to the potassium atoms.