Synthesis and Reactivity of N-Phosphanyl Phosphazenes

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Abstract
The reaction of phosphorus (III) halides, R′3−n PXn (X [dbnd] F, C1), with silyl azides, R3SiN3, are described. N-silyated halo- phosphazenes, R'3−n PX [dbnd]N[sbnd]SiR3, are only obtained with fluorophosphanes having bulky substituents. Usually azidophosphanes, R'3−nP(N3)n, are formed as intermediates. These may react both as azide and as phosphane components in the Staudinger reaction forming N[sbnd]phosphany 1 phosphazenes, R'2P[sbnd]N[dbnd]PR3, or azidophosphazenes, R'3−nP(N3)n[dbnd]NY (n = 1, 2), which can be converted into di- and triphosphazenes, R' P(N[dbnd]PR3)n[dbnd]NY. A one pot procedure for preparing N[sbnd]phosphanyl phosphazenes had been developed. Replacement as well as ooxidation reactions of Cl2P[sbnd]N[dbnd]PPh3 and its derivatives are presented.
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