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Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters

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Publication details

JournalChemical communications
DateAccepted/In press - 22 Jun 2021
DateE-pub ahead of print (current) - 22 Jun 2021
Number of pages5
Early online date22/06/21
Original languageEnglish


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.

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© The Royal Society of Chemistry 2021

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