Two new sterically demanding iminophosphonamine ligands (2,4,6-Me 3 C 6 H 2 NH)P(Ph 2)=N (C 6 H 2-2,4,6-Me 3) (1) and (2,6-iPr 2 C 6 H 3 NH)P(Ph 2)=N(C 6 H 2-2,4,6-Me 3) (2) and their lithium derivatives as tmeda adducts (Li•tmeda)[(2,4,6-Me 3 C 6 H 2)NP(Ph 2)=N(C 6 H 2-2,4,6-Me 3)] (3) and (Li•tmeda)[(2,6-iPr 2 C 6 H 3)NP(Ph 2)=N(C 6 H 2-2,4,6-Me 3)] (4), respectively are reported here. Compounds 1-4 have been investigated by 1 H, 13 C and 13 P{ 1 H} NMR spectroscopy. The 7 Li NMR for complexes 3 and 4 has also been reported. Utility of the ligands and their lithium derivatives have been shown in the synthesis of bis-homoleptic metal complexes M[Ph 2 P(NC 6 H 2-2,4,6-Me 3) 2 ] 2 (M = Co (5),C u(6) and Ni (7). Metal-bis-silylamide generated in situ was reacted with the ligand (for 5 and 6) or the lithium derivative of the ligand was reacted with the metal chloride (for 7). Molecular structure of compounds 1-7 has been elucidated by single crystal X-ray diffraction analyses. The complexes are formed in good yields and are highly lipophilic in a wide range of solvents.