Product analysis studies of the hydrolysis of [NP(OCH2CF3)2]3 in basic aqueous methanol revealed a nongeminal pathway for the removal of trifluoroethoxy groups from phosphorus. Kinetic studies of the removal of the first fluoroalkoxy group from [NP(OCH2CF3)2]3, [NP(OCH2C2F5)2]3, [NP(OCH2C3F7)2]3, [NP(OCH2CF3)2]4, and [NP(OCH2C3F7)2]4 in basic 25% aqueous diglyme showed that, for cyclic trimers, the ease of ligand displacement is in the order: OCH2C2F5 > OCH2CF3 > OCH2CF7. Cyclic tetramers hydrolyzed two to four times faster than the appropriate trimers. The mechanistic implications of these results are discussed.
All Science Journal Classification (ASJC) codes
- Colloid and Surface Chemistry