Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters

Journal article

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

Authors: Townrow, OPE; Weller, AS; Goicoechea, JM

• Publication status: Published
• Peer review status: Peer reviewed
• Publisher: Royal Society of Chemistry
• Journal: Chemical Communications
• Volume: 57
• Issue: 58
• Pages: 7132-7135
• Publication date: 2021-07-20
• DOI: 10.1039/d1cc02912f
• EISSN: 1364-548X
• ISSN: 1359-7345
• Language: English
• Keywords: Germanide; Reactivity (psychology); Crystal structure; Germanium; Nickel; Silicon; Crystallography; Cluster (spacecraft); Chemistry; Zintl phase