Reacting nickel(II)perchlorate with a bidentate P,N-ligand in methanol leads to P,C-bond cleavage and gives a five-coordinate nickel complex wherein the nickel(II) site is coordinated by a tridentate P,N,P-ligand and a bidentate N,C-ligand. The carbanion of the latter is the result of the P,C-bond cleaving process. The diamagnetic nickel(II) complex was characterized by means of elemental analysis, NMR spectroscopy, cyclic voltammetry and X-ray structure analysis.