Metalloid clusters have been in focus of interdisciplinary research for a long time. While there is a plethora of transition metal (carbonyl) clusters there are only a very limited examples of related main group metalloid clusters, including the most intriguing [Al50Cp*12], [Al77{N-(SiMe3)2}20],and [Ga84{N(SiMe3)2}20] (Cp* = pentamethylcyclopentadienyl). Interestingly, large, ligand stabilized intermetalloid transition metal (A) /main group metal (B) clusters [(AaBb)Ln] (a+b << n) are unknown. For many years we have been working on the development of a rational, wet-chemical synthetic access to well defined intermetallic complexes, clusters and nanoparticles which feature Hume Rothery Phase like combinations of metals (A2/B1), such as Cu/Al and Cu/Zn. Herein, we wish to present a recent break-though of our efforts. We will discuss synthesis, structure and bonding properties of the novel Cu/Al mixed metal hydride cluster [Cp*AlCu]6H4 (1  )and the giant intermetalloid Cu/Al-clusters [Cu43(AlCp*)12] (2  ) and [Cu43-xAlx(H)y(AlCp*)12] (3  ), which both reveal the magic number M55 core. Cluster 1  is readily accessible by reaction of [AlCp*]4 with [Ph3PCuH]6, while 2  is selectively obtained from the reaction of [AlCp*]4 with [CuMes]5 (Mes = Mesityl). Most interestingly, cluster 3  with a Cu/Al alloy core Cu43-xAlx is obtained by combination of 1  with [CuMes]5. The clusters 1-3  share the motive of AlCp* at the surface of the Mn inner core (n = 6, 43) which directly connects to Schn�ckel�s cluster [Al38(AlCp*)12] (M = Al, n = 38). This particular structural feature and our synthesis concept represents an important and quite rational link to the chemistry and ligand properties of carbenoid group-13 compounds ER (E = Al, Ga, In; R = steric demanding substituents, such as Cp*, bulky �-diketiminates etc.). We will present mechanistic studies on the cluster formation reactions and further preliminary results on our way to �molecular brass� and related Hume-Rothery intermetalloid clusters.

On the way to novel intermetalloid clusters

246th National Meeting (2013)

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