Selective One‐Pot Syntheses of Mixed Silicon‐Germanium Heteroadamantane Clusters

Si(x)Ge(y) alloys are emerging materials for modern semiconductor technology. Well‐defined model systems of the bulk structures aid in understanding their intrinsic characteristics. Three such model clusters have now been realized in the form of the Si( x )Ge( y ) heteroadamantanes [0], [1], and [2] through selective one‐pot syntheses starting from Me(2)GeCl(2), Si(2)Cl(6), and [nBu(4)N]Cl. Compound [0] contains six GeMe(2) and four SiSiCl(3) vertices, whereas one and two of the GeMe(2) groups are replaced by SiCl(2) moieties in compounds [1] and [2], respectively. Chloride‐ion‐mediated rearrangement quantitatively converts [2] into [1] at room temperature and finally into [0] at 60 °C, which is not only remarkable in view of the rigidity of these cage structures but also sheds light on the assembly mechanism.