When [PPN]SCN (1; PPN = [Ph3P-N-PPh3]) is treated with Me3Si-SCN in methanol, [PPN][H(NCS)(2)] (2), a hydrogen diisothiocyanate salt bearing the [H(NCS)(2)](-) anion, was generated, isolated, and fully characterized. Pure heavy E(NCS)(3) [E = Sb (3), Bi (4)] species were obtained from the reaction of EF3 and an excess of Me3Si-SCN, while the tetrahydrofuran (THF) solvates E(NCS)(3)center dot THF were isolated when the product was recrystallized from THF. When 2 equiv of 1 was combined with Me3Si-SCN and SbF3, [PPN](2)[Sb(NCS)(5)] (5) could be isolated. When 1 was added to BiF3, [PPN](2)[Bi(NCS)(3)(SCN)(2)center dot THF] (6 center dot THF), containing three SCN- ions coordinating via the N atom and two coordinating via the S atom, was isolated after recrystallization from THF. The structures of 1, 2, 3 center dot THF, 4 center dot THF, 5, and 6 center dot THF were determined. 3 center dot THF displayed a typical [3 + 3] coordination mode with a trigonal-pyramidal environment in the first coordination sphere of the Sb3+ ion, and the dianion of 5, [Sb(NCS)(5)](2-), featured a classical square-pyramidal molecular geometry around the Sb3+ ion with one additional Menshutkin-type interaction to one aryl ring of the [PPN](+) cation. 4 center dot THF exhibited a distorted pentagonal-bipyramidal structure within a two-dimensional network, while in 6 center dot THF, an octahedrally surrounded Bi3+ ion was observed.