Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters

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

doi:10.1039/D1CC02912F

Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters

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

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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 language	English
Number of pages	5
Journal	Chemical communications
Early online date	22 Jun 2021
DOIs	https://doi.org/10.1039/D1CC02912F
Publication status	E-pub ahead of print - 22 Jun 2021

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10.1039/D1CC02912FLicence: CC BY

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Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters
© The Royal Society of Chemistry 2021
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Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials
Weller, A. (Principal investigator)
EPSRC
1/01/20 → 31/03/22
Project: Research project (funded) › Research
Zintl–Ions as Molecular Analogues of Liquid Alloys for C–H Activation
Weller, A. (Principal investigator) & Goicoechea, J. (Principal investigator)
1/10/18 → 1/04/22
Project: Other project › Project from former institution

Cite this

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title = "Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters",

abstract = "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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AU - Townrow, Oliver P.E.

AU - Weller, Andrew

AU - Goicoechea, Jose M.

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N2 - 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.

AB - 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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M3 - Article

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JO - Chemical communications

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ER -

Cluster expansion and vertex substitution pathways in nickel germanide Zintl clusters

Abstract

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Projects

Putting Low Coordination into Practice by the Exploration of Metal-sigma-Interactions: Fundamentals, New Catalysts and Catalysis for New Materials

Zintl–Ions as Molecular Analogues of Liquid Alloys for C–H Activation

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