Unlike the reactions of (NPCI2H4 with simple amines, the fluorocyclophosphazenes,(NPF2)3f 4, react withmethylamine, n-butylamine, or dimethylamine with replacement of only one fluorine atom per phosphorus to yield products such as N4P4F5(NHMe)3, N4P4F4(NHMe)4, N4P4F5(NHC4H9)3, N4P4F5(NMe2)3, N4P4F4(NMe2)4, N3P3F4(NHMe)2, N3PrF4(NHC4HS)2, or N3P3F4(NMe2)2. This behavior cannot be ascribed to steric effects because nuclcophiles such as CF3CH2ONa, C6H5ONa, and (CH3)2NLi readily replace all the fluorine atoms. The results are more compatible with an explanation based on the poor leaving-group ability of fluoride combined with the low nucleophilicity of the free amines, compared with the higherleaving-group ability of chloride and the high nucleophilicity of alkoxides, aryl oxides, or metal amides.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry