Abstract
AbstractSchnöckel's [(AlCp*)4] and Jutzi's [SiCp*][B(C6F5)4] (Cp*=C5Me5) are landmarks in modern main‐group chemistry with diverse applications in synthesis and catalysis. Despite the isoelectronic relationship between the AlCp* and the [SiCp*]+fragments, their mutual reactivity is hitherto unknown. Here, we report on their reaction giving the complex salts [Cp*Si(AlCp*)3][WCA] ([WCA]−=[Al(ORF)4]−and [F{Al(ORF)3}2]−; RF=C(CF3)3). The tetrahedral [SiAl3]+core not only represents a rare example of a low‐valent silicon‐doped aluminium‐cluster, but also—due to its facile accessibility and high stability—provides a convenient preparative entry towards low‐valent Si−Al clusters in general. For example, an elusive binuclear [Si2(AlCp*)5]2+with extremely short Al−Si bonds and a high negative partial charge at the Si atoms was structurally characterised and its bonding situation analysed by DFT. Crystals of the isostructural [Ge2(AlCp*)5]2+dication were also obtained and represent the first mixed Al−Ge cluster.
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