Abstract: | Synthesis, Crystal Structures, and Vibrational Spectra of [(Ph3P)2N]2[(W6Cl )I ] · 2 Et2O · 2 CH2Cl2 and [(Ph3P)2N]2[(W6Cl )(NCS) ] · 2 CH2Cl2 By treatment of [(W6Cl)I]2– with (SCN)2 in dichloromethane at –20 °C the hexaisothiocyanato cluster anion [(W6Cl)(NCS)]2– is formed. X‐ray structure determinations have been performed on single crystals of [(Ph3P)2N]2[(W6Cl)I] · 2 CH2Cl2 · 2 Et2O ( 1 ) (triclinic, space group P1, a = 10.324(5), b = 14.908(3), c = 17.734(8) Å, α = 112.78(2)°, β = 99.13(3)°, γ = 92.02(3)°, Z = 1) and [(Ph3P)2N]2[(W6Cl)(NCS)] · 2 CH2Cl2 ( 2 ) (triclinic, space group P1, a = 11.115(2), b = 14.839(2), c = 17.036(3) Å, α = 104.46(1)°, β = 105.75(2)°, γ = 110.59(1)°, Z = 1). The thiocyanate ligands of 2 are bound exclusively via N atoms with W–N bond lengths of 2.091–2.107 Å, W–N–C angles of 173.1–176.9° and N–C–S angles of 178.1–179.3°. The vibrational spectra exhibit characteristic innerligand vibrations at 2067–2045 (νCN), 879–867 (νCS) and 490–482 (δNCS). Based on the molekular parameters of the X‐ray determination of 1 the vibrational spectra of the corresponding (n‐Bu4N) salt of 1 are assigned by normal coordinate analysis. The valence force constants are fd(WW) = 1.61, fd(WI) = 1.23 and fd(WCl) = 1.10 mdyn/Å. |