TY - JOUR
T1 - Small-molecule cyclic models for the synthesis of new polyphosphazenes
T2 - Side-group construction via lithiophenoxy derivatives
AU - Allcock, H. R.
AU - Evans, T. L.
AU - Fuller, T. J.
PY - 1980
Y1 - 1980
N2 - 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.
AB - 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.
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U2 - 10.1021/ic50206a047
DO - 10.1021/ic50206a047
M3 - Article
AN - SCOPUS:0006278328
SN - 0020-1669
VL - 19
SP - 1026
EP - 1030
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 4
ER -