Structure and decomposition of a Staudinger reaction intermediate [1-methyl-(or phenyl-)3-tris(dimethylamino)phosphoranylidenetriazene]

Abstract
Unstable intermediates (Me2N)3PN3R have been isolated from Staudinger reactions between hexamethylphosphorous triamide and methyl or phenyl azides. N.m.r. data strongly support the presence of a linear skeletal PN–NN framework in these compounds. Kinetic studies of the thermal decomposition of the phenyl derivative in methoxybenzene has afforded activation parameters (ΔH 95 KJ mol–1; ΔS–40 J mol–1 K–1) indicative of a constrained transition state for this decomposition.

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