Atom Exchange Versus Reconstruction: (Ge(x)As(4−x))(x−) (x=2, 3) as Building Blocks for the Supertetrahedral Zintl Cluster [Au(6)(Ge(3)As)(Ge(2)As(2))(3)](3−)

The Zintl anion (Ge(2)As(2))(2−) represents an isostructural and isoelectronic binary counterpart of yellow arsenic, yet without being studied with the same intensity so far. Upon introducing [(PPh(3))AuMe] into the 1,2‐diaminoethane (en) solution of (Ge(2)As(2))(2−), the heterometallic cluster anion [Au(6)(Ge(3)As)(Ge(2)As(2))(3)](3−) is obtained as its salt [K(crypt‐222)](3)[Au(6)(Ge(3)As)(Ge(2)As(2))(3)]⋅en⋅2 tol (1). The anion represents a rare example of a superpolyhedral Zintl cluster, and it comprises the largest number of Au atoms relative to main group (semi)metal atoms in such clusters. The overall supertetrahedral structure is based on a (non‐bonding) octahedron of six Au atoms that is face‐capped by four (Ge(x)As(4−x))(x−) (x=2, 3) units. The Au atoms bind to four main group atoms in a rectangular manner, and this way hold the four units together to form this unprecedented architecture. The presence of one (Ge(3)As)(3−) unit besides three (Ge(2)As(2))(2−) units as a consequence of an exchange reaction in solution was verified by detailed quantum chemical (DFT) calculations, which ruled out all other compositions besides [Au(6)(Ge(3)As)(Ge(2)As(2))(3)](3−). Reactions of the heavier homologues (Tt(2)Pn(2))(2−) (Tt=Sn, Pb; Pn=Sb, Bi) did not yield clusters corresponding to that in 1, but dimers of ternary nine‐vertex clusters, {[AuTt(5)Pn(3)](2)}(4−) (in 2–4; Tt/Pn=Sn/Sb, Sn/Bi, Pb/Sb), since the underlying pseudo‐tetrahedral units comprising heavier atoms do not tend to undergo the said exchange reactions as readily as (Ge(2)As(2))(2−), according to the DFT calculations.