X-Ray crystallographic and n.m.r. spectroscopic investigations show that the geminal amino derivative N3P3C14(NH2)2 on treatment with sodium n-propoxide in n-propanol gives the trans-compound, N3P3(NH2)2(OPrn)4, this being the first example of a rearrangement of this type in phosphazene chemistry.

The crystal structures of 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazatriene, N3P3(NH2)2C14 (1), and of 2-amino-2-triphenylphosphazenyl-4,4,6,6-tetrachlorocyclotriphosphazatriene, N3P3(NPPh3)-(NH2)C14 (2), have been determined and that of 2-triphenylphosphazenyl-2,4,4,6,6-pentachlorocyclotriphosphaz~:riene, N3P3(NPPh3)C15 (3), has been redeterminc,l by X-ray analysis. [Crystal data: For compound (1) the presence of geminal NH2 groups is established. Compound (2) is the first triphenylphosphazenyl derivative with a type III conformation, and compound (3) has a type I conformation. Structures are compared with those of related compounds. The relationship between conformation in the solid state as determined by dihedreal angles of the phosphazenyl substituent relative to the ring and the preferred conformations in solution as measured by 4j(pp) spin-spin coupling constants is discussed.

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2,2-N P (NH ) C 1 on complete alcoholysis i n the NaOR/ROH sysf?e2 g&? boih rearranged 2,4-N P3(NH2) (OR)4 and unrearranged 2,2-N P (NH2)2(OR)4 ( R = d e , CH2Cd3), w h i l s t f o r R = E t , Pr", 53 o n l y t h e r e a r r a n g e d d e r i v a t i v e s were observed. With N a O R i n e t h e r ( R = Pr") only r e a r r a n g e d d e r i v a t i v e s were o b t a i n e d , w h i l s t f o r R = CH2CF3, Ph o n l y t h e u n r e a r r a n g e d p r o d u c t s w e r e i s o l a t e d . From t h e ROH/pyridine s stem only unrearranged derivatives (R = studies suggested that the rearrangement occurred with t h e i n t r o d u c t i o n of t h e second alkoxy group. The

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