(N3P3Cl6VOCl3)-V-. results from the reaction between vanadium oxotrichloride and hexachlorotriphosphazene in dichloroethane. Vanadium oxotrichloride coordination with nitrogen atom in the phosphonitrile ring was detected from the IR spectrum of the product. Quantum-chemistry calculations for (NPX2)(3) (X=H, F, Cl, NH2) were carried out as well. A comparative study of some basic characteristics of the simple cyclotriphosphazenes' electronic structures was carried out. Quantum-chemistry calculations also were done for the complex of hexachlorophosphazene with vanadium oxotrichloride. It is shown that the nitrogen atom in phosphazenes plays an essential role for donor-acceptor interactions and is the most preferable atom for binding with a vanadium atom.