The chiral phosphanylamido ligand, {N(CHMePh)(PPh2)} -, has been introduced into co-ordination chemistry. As starting material the oily amines HN(R-*CHMePh)(PPh2) (1a) and HN(S-*CHMePh)(PPh2) (1b) were used. To reconfirm their absolute structure, 1b was oxidized with H2O2 in air to obtain HN(S-*CHMePh)(P(=O)Ph2) (2) as a solid compound. The solid-state structure of 2 was established by single-crystal X-ray diffraction. The lithium salts of both enantiomers Li{N(R-*CHMePh)(PPh2)} (3a) and Li{N(S-*CHMePh)(PPh2)} (3b) were prepared by deprotonation reaction of 1a,b. Compounds 3a,b were further reacted with zirconocen dichloride to give the chiral metallocenes [(η5-C 5H5)2Zr(Cl){η2N(R-*CHMePh) (PPh2)}] (4a) and [(η5-C5H 5)2Zr(Cl){η2-N(R-*CHMePh)(PPh 2)}] (4b). In an alternative approach to give chiral zirconium compounds, the neutral amine 1b was reacted with [(PhCH2) 4Zr] to give the enantiomeric pure complex [(PhCH2) 3Zr{η2-N(S-*CHMePh)(PPh2)}] (5). The solid-state structures of all zirconium complexes were determined by single-crystal X-ray diffraction. © The Rayal Society of Chemistry 2005.