The reaction of a non-symmetrical pyridine-NHC-phosphane (NĈP) ligand – generated in situ upon the deprotonation of the corresponding imidazolium salt – with equimolar amount of [Cu(NCMe)4](BF4) or Mn2(CO)10 leads to the formation of bimetallic complexes [Cu2(NĈP)2(NCMe)](BF4)2 and [Mn2(CO)7(NĈP)], respectively, in which the tridentate ligand exhibits an unusual µ-κ2Ĉ,N-M;κ1P-M coordination mode. According to NMR spectroscopy and mass spectrometry, the binuclear copper complex is in equilibrium in MeCN solution with two mononuclear species, namely [Cu(κ2Ĉ,P-NĈP)2](BF4) and [Cu(κ3-N,Ĉ,P-NĈP)(NCMe)](BF4).