Lewis acid stabilized OPI3: implications for the nature of free OPI3.

While reinvestigating the published synthesis of OPI(3), it became evident from the experiments that phosphoryl triodide may only be formed as an intermediate and that the end products of the reaction of OPCl(3) with LiI are P(V) oxides, PI(3), I(2), and LiCl. This is also in agreement with MP2/TZVPP calculations, which assign Delta(r)H degrees (Delta(r)G degrees ) [Delta(r)G degrees in CHCl(3)] for the disproportionation of OPI(3) as -7 (-18) [-17 kJ mol(-1)] (assuming P(4)O(10) as the P(V) oxide). The first products of this reaction visible in a low-temperature in situ (31)P NMR experiment are P(2)I(4) and PI(3), as well as traces of a compound that may be OPCl(2)I. By contrast, it was possible to prepare and structurally characterize Lewis acid [A] stabilized [A]<--OPX(3) adducts, where [A] is Al(OR(F))(3) for X=Br and Al(OR(F))(2)(mu-F)Al(OR(F))(3) for X=I (R(F)=C(CF(3))(3)). These adducts are formed on decomposition of PX(4) (+)[Al(OR(F))(4)](-); high yields of Br(3)PO-->Al(OR(F))(3) (delta((31)P)=-65) were obtained, while I(3)PO-->Al(OR(F))(3) (delta((31)P)=-337) and I(3)PO-->Al(OR(F))(2)(mu-F)Al(OR(F))(3) (delta((31)P)=-332) are only formed as by-products. The main product of the room-temperature decomposition of PI(4) (+)[Al(OR(F))(4)](-) is PI(4) (+)[(R(F)O)(3)Al(mu-F)Al(OR(F))(3)](-), which was also characterized by X-ray crystallography and was independently prepared from Ag(+)[(R(F)O)(3)Al(mu-F)Al(OR(F))(3)](-), PI(3), and I(2).