Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters

Oliver P.E. Townrow, Andrew Weller, Jose M. Goicoechea

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We describe the reactivity of the hypersilyl-functionalized Zintl cluster salt K[Ge9(Hyp)3] towards the nickel reagents Ni(COD)2 and Ni(Cp)2, which gives rise to markedly different compounds. In the case of Ni(COD)2, a dianionic sandwich-like compound [Ni{Ge9(Hyp)3}2]2− (1) was obtained, in line with a simple ligand substitution reaction of COD by [Ge9(Hyp)3]−. By contrast, when an analogous reaction with nickelocene was performed, vertex substitution of the [Ge9(Hyp)3]− precursor was observed, giving rise to the nine-vertex nido-cluster (Cp)Ni[Ge8(Hyp)3] (2). This is the first instance of vertex substitution at a hypersilyl-functionalized Zintl cluster cage. The electrochemical behavior of these compounds was explored and showed reversible redox behaviour for both clusters.
Original languageEnglish
Number of pages5
JournalChemical communications
Early online date22 Jun 2021
Publication statusE-pub ahead of print - 22 Jun 2021

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© The Royal Society of Chemistry 2021

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