A facile organometallic-induced cross-linking of copolymers of phosphazene

Incorporation of the organometallic fragments ML_n=CpFe(dppe)I and CpRu(PPh₃)₂Cl to the random copolymers [{NP(O₂C₁₂H₈)}_0.8{NP(OC₆H₄CH₂CN)₂}_0.15{NP(OC₆H₄CH₂CN)(OC₆H₅)}_0.05]_n (1) [{NP(O₂C₁₂H₈)}_0.55{NP(OC₆H₄CH₂CN)₂}_0.2{NP(OC₆H₄CH₂CN)(OC₆H₅)}_0.25]_n (2) produce the new compounds of the approximate composition: [{NP(O₂C₁₂H₈)}_x{NP(OC₆H₄CH₂CN·ML_n)₂}_y{NP(OC₆H₄CH₂CN·ML_n)(OC₆H₅)}_z]_n. The iron derivatives in solution undergo deprotonation of the dppe, probably caused by a polymeric matrix, which in turn causes a spontaneous cross-linking affording sparingly, soluble materials. Thermal analysis of the compounds using DSC and DTA techniques indicates that the incorporation of the organometallic fragment in the copolymer produces materials, which leave an amount of residue depending on the metal, as well as on the functionalization degree of the cyanide groups. Incorporation of the organometallic fragments to the polymer does not produce an improved conductivity in comparison to the insulator polymer without the organometallic fragment.