Dichloro-bis (indenyl) zirconium (IV) reacts with lithium derivatives of diphosphanes R2P–P (SiMe3) Li (R= tBu, Et2N, iPr2N) to form complexes with terminal phosphanylphosphido ligands–[Ind2Zr (Cl)-{(PSiMe3) P-PR2-κP1}]. These compounds are extremely sensitive towards moisture and oxygen. The solid state structures of these complexes were established by single crystal X-ray diffraction. The nitrogen bearing groups R (Et2N or ...