Details

Autor(en) / Beteiligte

• O’Donnell, Felix
• Wetmore, Stacey D.
• Gerken, Michael

Titel

Fluoride-Ion Donor Properties of AsF5

Ist Teil von

• Inorganic chemistry, 2024-04, Vol.63 (17), p.7619-7630

Ort / Verlag

American Chemical Society

Erscheinungsjahr

2024

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Arsenic pentafluoride undergoes ligand-induced autoionization in the presence of 1,10-phenanthroline (phen) in a SO2ClF solution to form the donor-stabilized [AsF4(phen)]­[AsF6] salt. Reacting [AsF4(phen)]­[AsF6] with the strong Lewis acid SbF5·SO2 yields the mixed arsenic–antimony salt [AsF4(phen)]­[Sb2F11]. These salts are the first examples of crystallographically characterized donor-stabilized [AsF4]+ cations. The analogous reaction of AsF5 and 2,2′-bipyridine (bipy) does not result in autoionization but leads to the formation of the neutral 2:1 adduct (AsF5)2·bipy. The gas-phase and solution fluoride-ion affinities of [AsF4]+ and [SbF4]+ were calculated, revealing them to be incredibly strong Lewis acids. Density functional theory calculations and natural bond orbital analysis show that significant electron-pair donation from phen to the As center in [AsF4(phen)]+ occurs and quenches the extreme electrophilicity of the [AsF4]+ cation.