The [PNP] ⁺ ‐ and [PPh ₄ ] ⁺ ‐Salts of Benzene‐ and Pentafluorobenzenesulfonic Acid (PNP = <i>bis</i> (triphenylphosphine)iminium; PPh ₄ = tetraphenylphosphonium)

The [PNP] + and [PPh 4 ] + salts of benzenesulfonic acid (HBS) and pentafluorobenzenesulfonic acid (HPFBS) are prepared by metathesis reactions using the sodium sulfonates, [PNP]Cl and [PPh 4 ]Cl, respectively. In the crystal structure of [PNP][BS] (orthorhombic, Z = 8, Pca 2 1 , a = 17.975(1), b = 17.375(1), c = 22.511(2) Å), the anions and the cations are arranged into layers, while in the fluorinated congener [PNP][PFBS] (monoclinic, Z = 4, P 2 1 / n , a = 15.557(1), b = 14.466(1), c = 16.868(1) Å, β = 108.460(3)°), they are uniformly distributed. The tetraphenyl phosphonium compounds [PPh 4 ][BS] (monoclinic, Z = 4, P 2 1 / n , a = 10.8151(3), b = 13.8325 (3), c = 16.6319 (5) Å, β = 107.09(1)°) and [PPh 4 ][PFBS] (triclinic, P‐1, Z = 2, a = 10.4984(6), b = 10.9087(6), c = 12.4014 (8) Å, α = 91.794 (2), β = 100.521(2), γ = 114.469(2)°) also show a balanced arrangement of cations and anions. All of the compounds are obtained as pure products, as confirmed by X‐ray powder diffraction measurements. Additionally, the data of infrared spectroscopy (IR) are provided. The synthetic accessibility, solubility, and crystallinity of these salts establish them as valuable starting materials for applications under nonaqueous or inert conditions.