Mass spectometric studies on cyclo- and poly-phosphazenes. Part 5. Oligomerization of octachlorocyclotetraphosphazatetraene N4P4Cl8
Abstract
The electron impact (e.i.) mass spectrometric behaviour of N4P4Cl8 shows that the main reaction process involves the formation of a heptachlorocyclophosphazene phosphorus cation [N4P4Cl7]+, which has a cyclotriphosphazatriene ring bearing a NPCl2 side group. This collapse of the cyclotetraphosphazatetraene structure to a cyclotriphosphazatriene moiety is a consequence of a ring-contraction reaction which yields more stable ionic trimeric phosphazene species. Ions [N3P3Cl5]+ are subsequently formed by the loss of the NPCl2 unit. Upon increasing the N4P4Cl8 vapour pressure to 0.65 Torr in the ionization chamber of the mass spectrometer, an oligomerization process takes place leading to chlorophosphazene oligomers, with oligomerization degree n of 12. Evidence is presented to show that the tetrameric ions [N4P4Cl8]˙+ formed from N4P8Cl8 under e.i. conditions have a different structure compared to analogous species produced during the gas-phase polymerization process of N3P3Cl6. This result gives further support to the mechanism proposed for gas-phase oligomerization of N3P3Cl6.