New Hofmann type complexes in the form of M(pp)(2)Ni(CN)(4) (where pp=1-phenylpiperazine and M=Ni, Co, Cd, Pd or Mn) have been prepared in powder form and their infrared spectra have been reported in the range of (4000-400) cm(-1). The thermal behaviours of these complexes have been investigated by differential thermal analysis (DTA) and thermo-gravimetric analysis (TGA). Ni(pp)(2)Ni(CN)(4) complex has been examined via transmission electron microscope (TEM). The results suggest that these compounds are similar in structure to Hofmann type complexes and their structures consist of polymeric layers |M-Ni(CN)(4)|(infinity) with the pp molecule bounded to the metal atom (M).