Structure and basicity. Part IV. Aminochlorocyclotriphosphazatrienes

Abstract

The basicities of a number of aminochlorocyclotriphosphazatrienes, N₃P₃Cl_6–nY_n(n= 1–4, and Y = NHEt, NHPrⁿ, NHPrⁱ, NHBu^t, NHPh, NH·C₆H₄·Me-p, NMe₂, NEt₂, or piperidino) have been measured in nitrobenzene. The geminal isomer of a tri- or tetra-amino-derivative is invariably a stronger base than the non-geminal isomer, and as this is expected from a priori reasoning about substituent effects, basicity measurements may reasonably be used to distinguish between these isomers. cis- and trans-Isomers have identical basicities within experimental error. The general relationships between structure and basicity in these compounds are discussed, and enable further structures, including those of two mixed chlorodimethylaminopiperidino-derivatives, to be assigned.