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The particularities of the chemical interaction in systems MIPO3 -MIIO(or Mn2O3)- MICl ( MI - Na, K; MII - Mg, Co, Ni, Zn) have been investigated at the temperature 1073 K and molar ratios P/ Mx = 1 or 2 and MICl/( MIPO3 + MIIO(or Mn2O3)) = 30. The conditions of formation of complex phosphates MІMIIPO4 and Na4Ni3(PO4)2P2O7 have been found. Influences of the nature of alkali and bivalent metals on the products composition were discussed. The advantages of chloride melts using (synthesis time reduction and temperature reducing) for preparing of complex phosphates were shown. The synthesized compounds have been characterized using the powder X-ray diffraction, Fourier transform infrared and diffuse reflectance spectroscopies. [ABSTRACT FROM AUTHOR]