Phosphoranyl (PH4) and diphosphine (P2H6+) radicals

Abstract

Theoretical computations for the ³¹P and ¹H isotropic coupling constants for PH₄ and [P₂H₆]⁺ radicals suggest that a species recently identified as PH₄ is more probably [P₂H₆]⁺. Comparisons with the data for structurally similar species strongly support this suggestion. In particular, the radical anions formed from Me₂(S)P–P(S) Me₂ and Et₂(S)P–P(S) Et₂ have e.s.r. spectra remarkably similar to that now assigned to [P₂H₆]⁺. E.s.r. results for acidic aqueous solutions containing both PH₃ and [PH₄]⁺ after exposure to ⁶⁰Co γ rays at 77 K give evidence for the formation of [P₂H₆]⁺ radicals during the annealing process.