[Ga6R8]2– (R = SiPh2Me): Eine metalloide Clusterverbindung mit einem unerwarteten Ga6‐Gerüst

[Ga₆R₈]^2– (R = SiPh₂Me): A Metalloid Cluster Compound with an Unexpected Ga₆‐Frame The reaction of a metastable solution of GaBr with a solution of LiSiPh₂Me in a toluene/THF mixture results in orange coloured crystals of [Ga₆(SiPh₂Me)₈]^2– · 2 [Li(THF)₄]⁺ ( 1 ). The unexpected structure of the planar Ga₆ frame (C_2h) could also be realized with the help of DFT calculation. DFT calculations furthermore show that 1 is energetically favoured against an octahedral Ga₆R₆^2– species and R₂. In contrast calculations for the similar Al and B species show that in these cases the octahedral entities are favoured. These results demonstrate that even for similar compounds of B, Al, and Ga Wade rules are too general and that they cannot predict the correct structure. Moreover the atomic arrangement within 1 shows that a structure is preferred which is also present in allotropic β‐Ga and that therefore clusters of this type should be called metalloid or more general elementoid.