Cluster Expansion versus Complex Formation: Coinage Metal Coordination to Silylated [Ge₉] Cages

Deltahedral nine-atom tetrel element Zintl clusters are promising building blocks for the straightforward solution-based synthesis of intermetalloid clusters through the reaction with organometallic compounds. Herein we report on novel coordination sites of metal-N-heterocyclic carbene (NHC) complexes to [Ge₉] clusters and unexpected cluster isomerization. We present the synthesis of a series of coinage metal-NHC complexes of silylated [Ge₉] clusters [NHCCu(η⁴-Ge₉{Si(TMS)₃}₃)] (1; TMS = trimethylsilyl) and [NHC^RM(η⁴-Ge₉{Si(TMS)₃}₂)]^- (2a, M = Cu, R = iPr; 3a, M = Cu, R = Mes; 4a, M = Cu, R = Dipp; 5a, M = Ag, R = Dipp; 6a, M = Au, R = Dipp), in which the coinage metals coordinate to open rectangular cluster faces and act as additional cluster vertex atoms. Besides representing promising intermediates on the way to larger intermetalloid clusters, the formation of compound 1 shows that Cu-NHC fragments also coordinate to the open-square Ge faces of the tris-silylated [Ge₉] clusters, contrasting the typical interactions with triangular faces of tris-silylated [Ge₉] clusters. In compounds 3a and 4a bearing bulky NHC moieties, an unusual silyl group substitution pattern is observed in contrast to 2a, which corresponds to the silyl group arrangement of other metal complexes of bis-silylated [Ge₉] clusters. In this context, potential silyl group migration mechanisms are discussed.