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

The phosphazene copolymers {[NP(O2C12H8)]0.5[NP(O–C6H4–CO2Prn)(O–C6H4–L)]0.5}n [L = CN (1), PPh2 (2)] and {[NP(O2C12H8)]0.6[NP(O–C6H4–CO2Prn)(O–C5H4N)]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–CO2Prn)(O–C6H4–CN)(W(CO)5)0.4]0.5}n (4), {[NP(O2C12H8)]0.5[NP(O-C6H4–CO2Prn)(O–C6H4–PPh2)(W(CO)5)0.7]0.5}n (5), {[NP(O2C12H8)]0.6[NP(O–C6H4–CO2Prn)(O–C5H4N–W(CO)5)]0.4}n (6a), and {[NP(O2C12H8)]0.6[NP(O–C6H4–CO2Prn)(O–C5H4N)(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 °C forming metal containing species that have a stabilizing effect on the polymeric matrices. The final residues up to 800 °C are of the order of30–50%.

Phosphazene copolymers carrying nitrile, pyridine and phosphine ligands have been synthesized by sequential substitution from [NPCl2]n. Their reactions with [W(MeOH)(CO)5] gives the corresponding tungsten carbonyl complexes, that undergo a complete decarbonylation below 300 °C forming metal containing species that have a stabilizing effect on the polymeric matrices.Figure optionsDownload as PowerPoint slide