113 / 2023-10-08 20:36:49

Dual Radical and Cationic Reactivity at Separated Atoms of Stable Distonic Radical Cations in Solution

radical • distonic radical cation • dicarbondiphosphide • phosphorus • carbene

Phosphorus in Synthetic Chemistry > 2) Phosphorus compounds as ligands

Distonic radical cations (DRCs) with spatially separated charge and radical sites have been proposed as key reactive intermediates in a number of intramolecular reactions. However, in contrast to the extensive gas phase studies, the condensed-phase isolable and structurally well-defined DRCs remain elusive. Herein we report the isolation of crystalline 1λ2,3λ2-1-phosphonia-3-phosphinyl-cyclohex-4-ene radical cations 3•+, which represent the first room-temperature stable and isolable DRCs that formed formally from ionization of biradicals, have been validated by crystallographic, spectroscopic, and computational characterization. These species as DRCs exhibit reactivities that differ inherently from conventional radical cations (CRCs), such as unprecedentedly unknown dual radical and cationic reactivity at separated atoms in one molecule and the conversion of a DRC to a CRC in the condensed-phase.