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[V@Ge8As4]3- and [Nb@Ge8As6]3-: encapsulation of electron-poor transition metal atoms
Stefan Mitzinger1, Lies Broeckaert, Werner Massa
1Philipps-Universität Marburg, Fachbereich Chemie and Wissenschaftliches Zentrum für Materialwissenschaften (WZMW), Hans-Meerwein-Straße 4, 35043 Marburg, Germany. dehnen@chemie.uni-marburg.de.
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) V(5+) 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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