Pyrolysis of (CF3)3P[N(CH3)2]2 in vacuo at 100°y ields (CF3)2FP[N(CH3)2]2, and at 215°( CF3)F2P[N(CH3)2]2 is formed. The difluorophosphorane (mp --17°) yields CF3P(0)[N(CH3)2]2 and CF3P0 31 2™ upon alkaline hydrolysis. The 19F nmr spectrum is temperature independent to-120°in keeping with a trigonal-bipyramidal structure with axial F substituents.The value of 2/pp (150 Hz) is typical of an equatorial CF3 group. The monofluorophosphorane (mp +15°) yields CF3H quantitatively and CF3P0 32~o n alkaline hydrolysis. Acid hydrolysis gave some CF3H but mainly (CF3)2P02" and CF3-P03H". Hydrogen chloride gave (CF3)2PFC12, (CF3)2PC13, and some unidentified compound. 19F nmr spectra of the monofluorophosphorane are temperature dependent showing an averaged 2Jpp coupling constant above room temperature and partially resolving to an equatorial (2/pp = 125 Hz) and an axial CF3 group. Additional secondary processes complicate the spectrum so that the axial coupling was not completely resolved, infrared and mass spectral data are reported for the new phosphoranes.
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