This thesis deals with adduct compounds of d-block elements with pnicogen chalcogenide cage molecules. The main topic of this work was to synthesize and characterize new compounds of the composition (MXn)m(Pn4Sx) with M = metal, X = halide and Pn = P, As. Adduct compounds of this type show a wide structural variety. With the early transition,
metal halides molecular adducts are formed. Until now, no molecular adduct compounds with arsenic or any adduct compounds containing titanium and PnxSy (Pn = P, As) cages have been known. We were the first to synthesize molecular
compounds of α-As4S4 and β-As4S4 cages with tantalum- and titaniumchloride with non-fragmented As4S4 cage molecules. These compounds are (TaCl5)(β-As4S4),
[(TaCl5)2(β-As4S4)]2(C7H8) and (TiCl4)(α-As4S4).
The dimer W2S2Cl8 forms co-crystals with phosphorus(V)-sulfide. Co-crystals of niobium(V)- and tantalum(V)-chloride with P4S10 had been reported before, but no route of synthesis which leads to a pure product has been known. Therefore, a procedure to synthesize these three isotopic structures was sought. Applying the same procedure to rhenium(V)-chlorid which shows the same structure
as the halides mentioned above, we expected a similar reaction. To our great surprise the result was a complex of the composition Re2[μ-P(S2)S3]2[PS2Cl2]2 containing a
formal rhenium-rhenium triple bond. The use of tetrahydrofuran as a solvent accidentally led to THF adduct compounds. On the one hand, single crystals of the long known MoOCl3(THF)2 were formed. Since there had not been any data for the solid phase in literature, experiments were performed on solid MoOCl3(THF)2. On the other hand the complex, W2(μ-S2)(μ-S)Cl6(THF)2 which contains a metal-metal single bond as well as a bridging persulfido ligand has been obtained. Reactions of late transition metal halides with pnicogen chalcogenides led to compounds in which matrices of the metal halide are stabilizing cage molecules of phosphorus or arsenic with sulfur or selenium. With regard to α-As4S4, adduct compounds of copper(I)-bromide and -iodide are known. Concerning copper(I)-chloride, however, no such structure had been known due to the thermodynamic sink of arsenic(III)-chloride. We were able to synthesize such compounds by the use of soft chemistry methods. With a mixture of mercury(II)- and copper(I)-iodide, we could obtain the first real adduct compound with Pn4Sx cage molecules containing mercury. These structures show highly disordered Pn4Sx cages. Together with (ZnI2)6(ZnS)(P4Sx) and Cd7I12S∙(As4Sx) these compounds form a family of inclusion compounds with great structural similarity. For a correct account of the prevalent electron density in these compounds, the intercalated cage molecules have to be described with anharmonic refinement.