The weak resonances at + 22 and + 49 ppm appearing in the 31P NMR spectrum of melts or solutions of (PPh)5 that have been attributed previously in the literature to “dimeric” and “monomeric phenylphosphorus” are caused by (PPh)6 and (PPh)4, respectively. This was proved by comparison with the 31P NMR parameters of related compounds and by 31P NMR spectroscopic investigation of authentic samples of (PPh)6 and (PPh)4, the latter of which was prepared in high yield from (Me3Si)PhP–PPh–PPh(SiMe3) and PhPCl2. (PEt)4 and mixed-substituted phenyl-ethyl-cyclotetraphosphanes exhibit similar chemical shifts as (PPh)4, corresponding mixed-substituted cyclohexaphosphanes have similar chemical shifts as (PPh)6. Generally, cyclophosphanes establish an equilibrium between (PR)n-species of different ring-size. Probably, the ring-interconversion proceeds via a multi-center mechanism. No 31P NMR spectroscopic evidence for the existence of free PPh or P2Ph2 under the conditions described could be detected. On thermolysis of (PEt)4 the existence of (PEt)3 was proved for the first time.

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