page_title: Aminophosphine
section_title: Aminophosphine chlorides
hierarchical_section_title: Aminophosphine / Aminophosphine chlorides
context_page_description: In organophosphorus chemistry, an aminophosphine is a compound with the formula R3−nPₙ where R = H or an organic substituent, and n = 0, 1, 2. At one extreme, the parent H₂PNH₂ is lightly studied and fragile, but at the other extreme trisphosphine is commonly available. Intermediate members are known, such as Ph₂PNPh. These compounds are typically colorless and reactive toward oxygen. They have pyramidal geometry at phosphorus.
context_section_description: The amination of phosphorus trihalides occur sequentially, with each amination proceeding more slowly than the preceding:
  PCl₃  +  2 HNMe₂   →   Me₂NPCl₂  +  [H₂NMe₂]Cl
  Me₂NPCl₂   +  2 HNMe₂   →   (Me₂N)₂PCl  +  [H₂NMe₂]Cl
  The mixed aminophosphine chlorides are readily isolated and are a versatile reagents. Commercially available derivatives include dimethylaminophosphorus dichloride and bis(dimethylamino)phosphorous chloride.
  Related aminophosphine fluorides compounds are available from trifluorophosphine.  Notable is the diphosphine MeN(PF₂)₂ prepared from methylamine:
  2 PF₃  +  3 H₂NMe   →   Me(PF₂)₂  +  2 [MeNH₃]F
  Me(PF₂)₂ 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:
  Ph₂PCl  +  2 HNEt₂   →   Ph₂PNEt₂  +  [H₂NEt₂]Cl
  Primary amines react with phosphorus(III) chlorides give aminophosphines with acidic α-NH centers:
  Ph₂PCl  +  2 H₂NR   →   Ph₂PN(H)R  +  [H₃NR]Cl
caption: Structure of Me2NPCl2.