Darstellung, Reaktionen und Kristallstrukturen von (Me3NCH2Ph)2 Fe2I6 und Fe2I4(SPPh3)2 · PhMe (Ph = C6H5, Me = CH3) / Preparation, Reactions, and Crystal Structure of (Me3NCH2Ph)2Fe2I6 and Fe2I4(SPPh3)2 · PhMe (Ph = C6H5, Me = CH3)

Abstract

The reaction of FeI2, with (Me3NCH2Ph)I in CH2Cl2 and with Ph3PS in toluene (molar ratios 1:1) yields (Me3NCH2Ph)2Fe2I6 (1) and Fe2I6(SPPh3)2·C6H5CH3 (2), respectively. The structures of 1 and 2 were determined from single crystal X-ray diffraction data. 1 crystallizes in the monoclinic space group P21/n with a = 895.7(2), b = 1400.5(2), c = 1360.6(3) pm. β = 95.82(2)°, Z = 2. The anion of 1, Fe2I6 2-, has edge-sharing double-tetrahedra. The bridging and terminal F e - I bond lengths were found to be 269.9/270.7 and 260.3/258.6 pm, respectively (Fe-Fe: 358.2 pm). 2 crystallizes in the triclinic space group P1̄ with a = 987.6(1), b = 1119.3(1), c = 1159.4(1) pm, α = 101.10(1), β = 99.15(1), γ = 102.83(1)°, Z = 1. The molecules of 2 consist of centrosymmetric dinuclear Fe2I2 units (like for Fe2I6 2- in 1), with F e - I distances of 266.4 and 273.4 pm. The distorted tetrahedra around Fe are completed by an iodide ion (Fe-I: 256.9 pm) and Ph3PS with the sulfur as donor atom. The Fe-Fe distance was found to be 339.7 pm.