The reactions of N‐dichlorophosphoryl‐P‐trichlorophosphazene Cl₃PNP(O)Cl₂ (1) with benzylmagnesium bromide, 2‐phenylethylmagnesium bromide, trimethylsilylmethylmagnesium chloride, n‐butylmagnesium bromide, cyclohexylmagnesium bromide, cyclopentylmagnesium bromide, tert‐butylmagnesium bromide, iso‐propylmagnesium bromide, and ethylmagnesium bromide were studied. Tri‐ and pentaalkyl phosphazenes were obtained in very poor yield from trimethylsilylmethylmagnesium chloride and cyclohexylmagnesium bromide, respectively. Trialkylphosphoryl compounds formed from benzyl‐, 2‐phenylethyl‐, and n‐butylmagnesium bromide. No phosphorus compound could be isolated from the reaction of 1 with t‐butyl‐, cyclopentyl‐, iso‐propyl‐, and ethylmagnesium bromide. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:413–416, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10153