Reactions of the dilithiated diols RCH2P(S)(CH2OLi)(2) [R = Fe (1), Ph (2) (Fc = ferrocenyl)] with N3P3F6 in equimolar ratios at -80 OC result exclusively in the formation of two structural isomers :of ansa-substituted compounds, endo-RCH2P(S)(CH2O)(2)[P(F)N](2)(F2PN) [R = Fe (3a), Ph (4a)] and exo-RCH2P(S)(CH2O)(2)[P(F)N](2)(F2PN) [R = Fe (3b), Ph (4b)], which are separated by column chromatography. Increasing the reaction temperature to -40 degrees C results in more of the exo isomers 3b and 4b at the expense of the endo isomers. The formation of the ansa-substituted compounds is found to depend on the dilithiation of the diols, as a reaction of the silylated phosphine sulfide FcCH(2)P(S)(CH2OSiMe3)(2) (5) With N3P3F6 in the presence of CsF does not yield either 3a or 3b but instead fives the spiro isomer [FcCH(2)P(S)(CH2O)(2)PN](F2PN)(2) (6) as the disubstitution product of N3P3F6. The ansa isomers 3a and 3b an transformed into the spiro compound 6 in the presence of catalytic amounts of CsF at room temperature in THF, while 4a and 4b are transformed into the spiro compound [PhCH2P(S)(CH2O)(2)PN](F2PN)(2) (7) under similar conditions. The novel conversions of ansa-substituted phosphazenes into spirocyclic phosphazenes Were monitored by time-dependent P-31 NMR spectroscopy. The effect of temperature on a transformation was studied by carrying out reactions at various temperatures in the range from -60 to +33 degrees C for 3b. In addition, compounds 3a, 3b, 4a, and 6 were structurally characterized. In the case of the ansa compounds, the nitrogen atom flanked by the bridging phosphorus sites was found to deviate significantly from the plane defined by the five remaining atoms of the phosphazene ring.