A crystalline phosphinyl radical cation.

One-electron oxidation of a readily available phosphaalkene derived from a cyclic (alkyl)(amino)carbene affords a phosphorus-centered radical cation that is indefinitely stable both in solution and in the solid state, allowing a single X-ray diffraction study to be performed. This species can be regarded as a phosphinyl radical bearing a cationic substituent or, alternatively, as a carbene-stabilized phospheniumyl radical (carbene-RP(+*)).