We report the synthesis and characterization of the cluster anions [GePd{SiPr}] (1) with a core of face-fused twinned icosahedra, GePd, and two sets of three PrSi-substituents positioned in "eclipsed" geometry. The new anion is a positional isomer of the recently reported "staggered" stannyl-ligated counterpart [GePd{SnPr}] (2), showing the possibility to find such positional isomerism in Zintl clusters. Both anions are characterized by single-crystal X-ray diffraction, H and C NMR, and negative-ion ESI-MS. Using relativistic DFT calculations, we elucidate and discuss the reasons for the different positioning of the ligands in the stannyl- and silyl-functionalized species.
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| http://dx.doi.org/10.1021/jacs.7b08562 | DOI Listing |
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