The amination of phosphorus trihalides occur sequentially, with each amination proceeding more slowly than the preceding:
:PCl  +  2 HNMe   →   MeNPCl  +  [HNMe]Cl
:MeNPCl   +  2 HNMe   →   (MeN)PCl  +  [HNMe]Cl
With bulky amines like diisopropylamine, the selectivity for the monosubstitution improves.
Commercially available aminophosphine chlorides include dimethylaminophosphorus dichloride and bis(dimethylamino)phosphorus chloride.
Related aminophosphine fluorides compounds are available from trifluorophosphine.  The diphosphine MeN(PF) is prepared from methylamine:
:2 PF  +  3 MeNH   →   MeN(PF)  +  2 [MeNH]F
Me(PF) is used as a bridging ligand in organometallic chemistry.
Substituted aminophosphines are generally prepared from organophosphorus chlorides and amines. The method is used to prepare ligands for homogeneous catalysis.  Chlorodiphenylphosphine and diethylamine react to give an aminophosphine:
:PhPCl  +  2 HNEt   →   PhPNEt  +  [HNEt]Cl
Primary amines react with phosphorus(III) chlorides give aminophosphines with acidic α-NH centers:
:PhPCl  +  2 HNR   →   PhPN(H)R  +  [HNR]Cl