Synthesis and thermal decarbonylation of W(CO)(5) complexes supported by nitrile, pyridine or phosphine ligands to poly-spirophosphazene random copolymers carrying O-C6H5-CO2Pr groups

Abstract

The phosphazene copolymers {[NP(O2C12H8)](0.5)[NP(O-C6H4-CO2Pr")(O-C6H4-L)](0.5)}(n) [L=CN (1), PPh2, (2)] and {[NP(O2C12H8)](0.6)[NP(O-C6H4-CO2Pr")(O-C6H4-L)](0.4)}(n) (3) have been synthesized by sequential substitution from [NPCl2](n),. Their reactions with [W(MeOH)(CO)(5)] gives the corresponding tungsten carbonyl complexes {[NP(O2C12H8)](0.5)[NP(O-C6H4-CO2Pr")(O-C6H4-CN)(W(CO)(5))(0.4)](0.5)}(n) (4), {[NP(O2C12H8)](0.5)[NP(O-C6H4-CO2Pr")(O-C6H4-PPh2)(W(CO)(5))(0.7)](0.5)}(n) (5), {[NP(O2C12H8)](0.5)[NP(O-C6H4-CO2Pr")(O-C6H4N-W(CO)(5))](0.4)}(n) (6a), and {[NP(O2C12H8)](0.5)[NP(O-C6H4-CO2Pr")(O-C6H4N)(W(CO)(5))(0.4)](0.4)}(n) (6b), that have been fully characterized by IR and NMR spectroscopies. The thermal properties (TGA and DSC) of the polymeric complexes showed that they are high glass transition materials that undergo a complete decarbonylation below 300 degrees C forming metal containing species that have a stabilizing effect on the polymeric matrices. The final residues up to 800 degrees C are of the order of 30-50%.