Tertiary Phosphine and Arsine Complexes of Phosphorus Pentafluoride: Synthesis, Properties, and Electronic Structures

The reaction of PMe₃ or PPh₃ with PF₅ in anhydrous CH₂Cl₂ or hexane forms the white, moisture-sensitive complexes [PF₅(PR₃)] (R = Me, Ph). Similar reactions involving the diphosphines o-C₆H₄(PR₂)₂ afford the complexes [PF₄{o-C₆H₄(PR₂)₂}][PF₆]. The X-ray structures of [PF₅(PR₃)] and [PF₄{o-C₆H₄(PMe₂)₂}][PF₆] show pseudo-octahedral fluorophosphorus centers. Multinuclear NMR spectra (¹H, ¹⁹F{¹H}, ³¹P{¹H}) show that in solution in CH₂Cl₂/CD₂Cl₂ the structures determined crystallographically are the only species present for [PF₅(PMe₃)] and [PF₄{o-C₆H₄(PMe₂)₂}][PF₆] but that [PF₅(PPh₃)] and [PF₄{o-C₆H₄(PPh₂)₂}][PF₆] exhibit reversible dissociation of the phosphine at ambient temperatures, although exchange slows at low temperatures. The complex ¹⁹F{¹H} and ³¹P{¹H} NMR spectra have been analyzed, including those of the cation [PF₄{o-C₆H₄(PMe₂)₂}]⁺, which is a second-order AA'XX'B₂M spin system. The unstable [PF₅(AsMe₃)], which decomposes in a few hours at ambient temperatures, has also been isolated and spectroscopically characterized; neither AsPh₃ nor SbEt₃ forms similar complexes. The electronic structures of the PF₅ complexes have been explored by DFT calculations. The DFT optimized geometries for [PF₅(PMe₃)], [PF₅(PPh₃)], and [PF₄{o-C₆H₄(PMe₂)₂}]⁺ are in good agreement with their respective crystal structure geometries. DFT calculations on the PF₅-L complexes reveal the P-L bond strength falls with L in the order PMe₃ > PPh₃ > AsMe₃, consistent with the experimentally observed stabilities, and in the PF₅-L complexes, electron transfer from L to PF₅ on forming these complexes also follows the order PMe₃ > PPh₃ ≈ AsMe₃.