Abstract The hindered reactivity of [PhP (CH 2 Py) 2 LiCl] 2 (2) compared to the coordination behavior of the lithium chloride free ligand PhP (CH 2 Py) 2 (Py= 2-pyridyl)(1) could be elucidated by means of experimental electron density studies. According to the successful synthesis of metal complexes containing the dianionic Janus Head ligand [PhP (CHPy) 2] 2– , the formation and the coordination pattern of the monoanionic ligand [PhP {C (H) Py}(CH ...