Stable germanium(II)-dithiocarbamate complexes Ge[S2C(NR2)]2 (R = Me, Et) have been obtained from GeCl2 · dioxane and Na[S2C(NR2)]. As an intermediate, Ge(Cl)[S2C(NEt2)] also could be isolated. Likewise, Ge[S2PMe2]2 was synthesized from GeCl2 · dioxane and Na[S2PMe2] and characterized by X-ray structure analysis. The germanium atom acts as a spiro-center for four sulfur atoms in a distorted ψ-trigonal bipyramidal configuration which is established by two anisobidentate dithiophosphinate ligands. The axial Ge—S bonds are significantly longer (mean: 2.722 A) than the equatorial ones (mean: 2.415 A). The variation in the axial bonds is more pronounced (0.058 A) than in the equatorial (0.013 A) Ge—S bonds, but this effect is much smaller than in the comparable Ge[(PMe2)2CPMe2]2 complex.
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