New 1, 3, 2-diazaphospholidine-4, 5-diimines were synthesized by condensation of lithiated oxalamidines with PCl3 or PhPCl2, and characterized by spectral and analytic data. The products react selectively with [(nbd)W(CO)4], [Mo(CO)6], or [(PhCN)2PdCl2] to give stable complexes, in which the heterocycle binds as chelating, bidentate ligand through the nitrogen atoms of the diimine unit. Formation of P-bound or dinuclear complexes was not observed. Reaction with PCl3 or AsCl3 in the presence of SnCl2 as reducing agent was unspecific. Evidence for the formation of bicyclic products arising from formal [4+1] cycloaddition between the diimine unit and a transient pnictogen(I) species was not obtained, and only a diimine complex of SnCl4 was isolated in moderate yield. Single-crystal X-ray diffraction studies reveal that coordination of the diimine unit induces a substantial structural distortion of the ligand framework, which allows to explain the occurrence of substantial 31P coordination shifts despite the absence of a direct metal-phosphorus bond.