Staudinger Reaction as a Way Out To Avoid Cyclization in the Reaction of Silylated Dichloro(hydrazino)phosphane with Trimethylsilyl Azide

Reaction of dichloro‐ N , N ′, N′ ‐[tris(trimethylsilyl)]hydrazinophosphane ( 1 ) with Me 3 SiN 3 leads after an initial chlorine/azide exchange in a Staudinger reaction to a new phosphorus azide. The in situ formed phosphoranimine reacts with GaCl 3 by Me 3 SiCl elimination, resulting in a phosphoranimino–dichlorogallane, which dimerizes to a Ga 2 N 2 ‐four‐membered ring. The overall reaction at ambient temperature represents a fast and clean high‐yielding reaction (reaction time 2 h). The dimer of the formed azido–phosphoranimino–dichlorogallane was fully characterized and shown to be stable to temperatures above 103 °C.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)