Two new sterically demanding iminophosphonamine ligands (2,4,6-Me₃C₆H₂NH)P(Ph₂)=N (C₆H₂-2,4,6-Me₃) (1) and (2,6-iPr₂C₂H₃NH)P(Ph₂)=N(C₆H₂-2,4,6-Me₃) (2) and their lithium derivatives as tmeda adducts (Li·tmeda)[(2,4,6-Me₃C₆H₂)NP(Ph₂)=N(C₆H₂-2,4,6-Me₃)] (3) and (Li·tmeda)[(2,6-iPr₂C₂H₃)NP(Ph₂)=N(C₆H₂-2,4,6-Me₃)] (4), respectively are reported here. Compounds 1–4 have been investigated by ¹H, ¹³C and ¹³P{¹H} NMR spectroscopy. The ⁷Li 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[Ph₂P(NC₆H₂-2,4,6-Me₃)₂]₂ (M = Co (5), Cu (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.