GAS-PHASE REACTIONS OF H3PF2 - SYNTHESIS OF THE MONOHALOGENOPHOSPHANES H2PF AND H2PCL

Gas phase reactions of H3PF2 at less-than-or-equal-to 10 mbar with hydrides (B2H6, HSi(CH3)3, HSn(CH3)3), amines (H3N, N(CH3)3) and electrophilic halides of B, Si and Ti in the beam of an IR interferometer have been investigated with a time delay of 15 sec. between successive measurements. Gas/solid phase reactions of H3PF2 with KF and AlCl3 and reactions of H2PF3 and HPF, have been studied similarly. With H3N, N(CH3), and electrophilic halides, H3PF2 was converted into its dehydrofluorination product H2PF. This eliminates further HF in the presence of H3N or N(CH3)3, while BCl3 or TiCl4 yield the hitherto unknown H2PCl. The IR spectra of the short-lived species H2PF and H2PCI as well as their deuterated isotopomers, which reveal at room temperature and less-than-or-equal-to 10 mbar a halflife time of less-than-or-equal-to 12 min. and less-than-or-equal-to 50 sec. respectively, were recorded and analysed in order to characterize the novel species.