[V@Ge8As4]3− and [Nb@Ge8As6]3−: encapsulation of electron-poor transition metal atoms

Stefan Mitzinger; Lies Broeckaert; Werner Massa; Florian Weigend; Stefanie Dehnen

doi:10.1039/C4CC10086G

[V@Ge₈As₄]³⁻ and [Nb@Ge₈As₆]³⁻: encapsulation of electron-poor transition metal atoms†

Stefan Mitzinger,^a Lies Broeckaert,^ac Werner Massa,^a Florian Weigend*^bc and Stefanie Dehnen*^a

* Corresponding authors

^a Philipps-Universität Marburg, Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Hans-Meerwein-Straße 4, 35043 Marburg, Germany
E-mail: dehnen@chemie.uni-marburg.de
Fax: +49 6421 2825653
Tel: +49 6421 2825751

^b Institut für Nanotechnologie, Karlsruher Institut für Technologie (KIT), Hermann-von-Helmholtz-Platz 1, 76344 Eggenstein-Leopoldshafen, Germany

^c Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT), Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany

Abstract

[K([2.2.2]crypt)]⁺ salts of [V@Ge₈As₄]³⁻ and [Nb@Ge₈As₆]³⁻ were obtained by extraction of quaternary phases with en/[2.2.2]crypt. The V–Ge–As anion is the first Zintl anion incorporating a (formal) V⁵⁺ cation, thus the smallest cation ever embedded within a main group (semi-)metal cage. It represents the second example of a novel 12-vertex cluster architecture. The bonding situation was elucidated by quantum chemistry, also allowing for a precise assignment of Ge vs. As atoms, being indistinguishable by X-ray diffraction.

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DOI: https://doi.org/10.1039/C4CC10086G
Article type: Communication
Submitted: 17 Dec 2014
Accepted: 28 Jan 2015
First published: 29 Jan 2015
This article is Open Access

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Chem. Commun., 2015,51, 3866-3869

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[V@Ge₈As₄]³⁻ and [Nb@Ge₈As₆]³⁻: encapsulation of electron-poor transition metal atoms

S. Mitzinger, L. Broeckaert, W. Massa, F. Weigend and S. Dehnen, Chem. Commun., 2015, 51, 3866 DOI: 10.1039/C4CC10086G

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Chemical Communications

[V@Ge₈As₄]³⁻ and [Nb@Ge₈As₆]³⁻: encapsulation of electron-poor transition metal atoms†

Abstract

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[V@Ge₈As₄]³⁻ and [Nb@Ge₈As₆]³⁻: encapsulation of electron-poor transition metal atoms

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