Novel Approach for the Synthesis of Chlorophosphazene Cycles with a Defined Size via Controlled Cyclization of Linear Oligodichlorophosphazenes [Cl(PCl(2)=N)(n)–PCl(3)](+)[PCl(6)](−)

Despite a significant number of investigations in the field of phosphazene chemistry, the formation mechanism of this class of cyclic compounds is still poorly studied. At the same time, a thorough understanding of this process is necessary, both for the direct production of phosphazene rings of a given size and for the controlled cyclization reaction when it is secondary and undesirable. We synthesized a series of short linear phosphazene oligomers with the general formula Cl[PCl2=N]n–PCl(3)(+)PCl(6)(–) and studied their tendency to form cyclic structures under the influence of elevated temperatures or in the presence of nitrogen-containing agents, such as hexamethyldisilazane (HMDS) or ammonium chloride. It was established that linear oligophosphazenes are inert when heated in the absence of the mentioned cyclization agents, and the formation of cyclic products occurs only when these agents are involved in the process. The ability to obtain the desired size phosphazene cycle from corresponding linear chains is shown for the first time. Known obstacles, such as side interaction with the PCl(6)(–) counterion and a tendency of longer chains to undergo crosslinking elongation instead of cyclization are still relevant, and ways to overcome them are being discussed.