Synthesis and thermal decarbonylation of W(CO) 5 complexes supported by nitrile, pyridine or phosphine ligands to poly-spirophosphazene random copolymers carrying O–C 6H 5–CO 2Pr groups

Abstract

The phosphazene copolymers {[NP(O 2C 12H 8)] 0.5[NP(O–C 6H 4–CO 2Pr n )(O–C 6H 4–L)] 0.5} n [L = CN ( 1), PPh 2 ( 2)] and {[NP(O 2C 12H 8)] 0.6[NP(O–C 6H 4–CO 2Pr n )(O–C 5H 4N)] 0.4} n ( 3) have been synthesized by sequential substitution from [NPCl 2] n . Their reactions with [W(MeOH)(CO) 5] gives the corresponding tungsten carbonyl complexes {[NP(O 2C 12H 8)] 0.5[NP(O–C 6H 4–CO 2Pr n )(O–C 6H 4–CN)(W(CO) 5) 0.4] 0.5} n ( 4), {[NP(O 2C 12H 8)] 0.5[NP(O-C 6H 4–CO 2Pr n )(O–C 6H 4–PPh 2)(W(CO) 5) 0.7] 0.5} n ( 5), {[NP(O 2C 12H 8)] 0.6[NP(O–C 6H 4–CO 2Pr n )(O–C 5H 4N–W(CO) 5)] 0.4} n ( 6a), and {[NP(O 2C 12H 8)] 0.6[NP(O–C 6H 4–CO 2Pr n )(O–C 5H 4N)(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%.