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The preparation and x-ray structure of [P(C2H5)4]+[N3]− and the attempted preparation of [PH4]+[N3]−

✍ Scribed by Thomas M. Klapötke; Axel Schulz; Peter S. White; Margaret J. Crawford

Publisher
John Wiley and Sons
Year
1998
Tongue
English
Weight
171 KB
Volume
9
Category
Article
ISSN
1042-7163

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✦ Synopsis

Tetraethylphosphonium azide, [P(C 2 H 5 ) 4 ] ‫ם‬ [N 3 ] ‫מ‬ , was prepared from tetraethyl phosphonium bromide and silver azide. Single crystals of [P(C 2 H 5 ) 4 ] ‫ם‬ [N 3 ] ‫מ‬ were grown from dichloromethane/THF (10:1) solution. The structure was determined by single-crystal X-ray diffraction analysis. [P(C 2 H 5 ) 4 ] ‫ם‬ [N 3 ] ‫מ‬ crystallizes in the monoclinic space group C 2/c with Z ‫ס‬ 4 and unit cell dimensions a ‫ס‬ 12.961(6), b ‫ס‬ 6.835(3), c ‫ס‬ 12.378(6) A ˚, and b ‫ס‬ 100.57(4)Њ. The attempted preparation of phosphonium azide [PH 4 ] ‫ם‬ [N 3 ] ‫מ‬ from phosphonium iodide and silver azide lead instead to the formation of PH 3 and HN 3 . The instability of [PH 4 ] ‫ם‬ [N 3 ] ‫מ‬ with respect to PH 3 and HN 3 is in accord with thermodynamic considerations according to which the reaction PH 3 (g) and HN 3 (g) to yield [PH 4 ] ‫ם‬ [N 3 ] ‫מ‬ is thermodynamically unfavorable.

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