New and unusual metallocenylphosphazene high Dolvmers have been Prepared by the thermal ring-opening polymerization of metallocene-substituted cyclotriphosphazene derivatives. The transannular-linked cyclic trimers [N3P3F4(η-C5H4)2M] (la, M = Fe; lb, M = Ru) and the monosubstituted compounds [N3P3F5(η-C5H4)M(η-C6H5)] (2a, 2b) serve both as reaction model compounds and as “monomers” for the analogous high polymeric derivatives 3a, 3b, and 8a, 8b. The hydrolytically unstable P—F bonds in the trimers and high polymers were replaced by treatment with sodium trifluoroethoxide to yield the corresponding air-stable trimeric and polymeric metallocenyl(trifluoroethoxy)phosphazenes (4a, 4b, 9a, 9b). Compounds la and lb were also copolymerized to yield a 1:1 copolymer which, after reaction with sodium trifluoroethoxide, yielded [N3P3(OCH2CF3)4(η-C5H4)2Fe-N3P3(OCH2CF3)4(ηC5H4)2Ru]n (7). The properties, structure, and characterization of these new organometallic polyphosphazenes are discussed, together with the mechanism of thermal polymerization of cyclic phosphazenes.
All Science Journal Classification (ASJC) codes
- Organic Chemistry
- Polymers and Plastics
- Inorganic Chemistry
- Materials Chemistry