Hexakis(p-lithiophenoxy)cyclotriphosphazene, [NP(OC6H4Li-p)2]3 (IV), has been synthesized as an intermediate for the covalent attachment of metallo, phosphino, carboxylato, alkyl, or tertiary alcohol units to the side-group structure. These reactions are models for the preparation of the corresponding phosphazene high polymers. Intermediate IV was prepared by the metal-halogen exchange reaction between [NP(OC6H4Br-p)2]3 (III) or [NP(OC6H4I-p)2]3 and n-butyllithium in tetrahydrofuran at -40 to -60 °C. The subsequent interaction of IV with deuterium oxide, diphenylchlorophosphine, carbon dioxide, butyl bromide, benzophenone, triphenyltin chloride, or (triphenylphosphine)gold(I) chloride yielded the para-substituted derivatives [NP(OC6H4D)2]3 (VII), [NP(OC6H4P(C6H5)2)2]3 (VIII), [NP(OC6H4COOH)2]3 (IX), [NP(OC6H4C4H9)2]3 (X), [NP(OC6H4C(OH)(C6H5)2)2]3 (XI), [NP(OC6H4Sn(C6H5)3)2]3 (XII), and [NP(OC6H4AuP(C6H5)3)2]3 (XIII), respectively. Compounds VII-XIII cannot be obtained readily by other synthetic routes. For example, the reaction of III with NaP(C6H5)2 is a less efficient route to the preparation of VIII. Compound VIII is a model coordination carrier species for transitionmetal catalysts. The possible extension of these reactions to linear phosphazene high polymers is discussed.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry