The Cation Cluster of Heavier Group 14 Elements:  A Free Germyl Cation with Trishomoaromaticity

Abstract

The heavier group 14 element cation cluster compound, [(tBu3Si)6Ge10I]+.TTFPB- (3+. TTFPB-; TTFPB- = tetrakis(2,3,5,6-tetrafluorophenyl)borate), was unexpectedly obtained by thermolysis of in situ prepared iodocyclotrigermene, (tBu3Si)3Ge3I, in toluene in the presence of KI and K+.TTFPB-. The molecular structure of 3+.TTFPB- has been unambiguously determined by X-ray crystallography, showing that 3+ is a free germyl cation. The three "naked" cationic germanium atoms in the framework constitute a three-center two-electron (3c-2e) bond with a trishomocyclotrigermenylium character, which is well-supported by a theoretical calculation on the model compound Ge10H7+.

Metal‐Rich, Neutral and Cationic Organotin Clusters

“…[11][12][13][14][15] Nonetheless, there is only one example (the anion [Ge 9 {N(SiMe 3 ) 2 } 3 ] À ) [16] 4 ]. [17] Herein we report three new element-rich organo clusters of tin whose structures are analogous to, or derived from, the E 9 xÀ Zintl framework. These are the neutral Sn 9 [18] in hot toluene and was isolated as dark red, almost black crystals.…”

[Au3Ge45]9−—A Binary Anion Containing a {Ge45} Cluster

“…[21] The bond character of the Ge54-Ge55-Ge56 triangle compares well to a similar triangle of Ge atoms (Ge4-Ge5-Ge6) in the cationic cluster [Ge 10 -(SitBu 3 ) 6 I] + (3 a, Figure 2), which shows a comparable atomic arrangement with the difference that bridging Ge atoms Ge7 to Ge9 in 3 a are fourfold-coordinated, whereas the corresponding atoms Ge57 to Ge59 in 2 a are threefoldcoordinated. The contacts within the three-membered rings Ge4 to Ge6 in 3 a have been described as a three-center, twoelectron bond; [22] these contacts (3.254-3.264 ) are considerably longer than their counterparts Ge54 to Ge56 in 2 a. Therefore, the description of a three-center, two-electron bond applies even better for 2 a.…”

[Au3Ge45]9− – ein binäres Cluster‐Anion mit einer {Ge45}‐Einheit

“…[21] Die Bindung in diesem GeDreieck Ge54-Ge55-Ge56 ist vergleichbar mit dem GeDreieck Ge4-Ge5-Ge6 im kationischen Cluster [Ge 10 -(SitBu 3 ) 6 I] + (3 a, Abbildung 2). [22] Dieser Cluster zeigt eine ähnliche Atomanordnung mit dem Unterschied, dass die verbrückenden Ge-Atome Ge7 bis Ge9 in 3 a vierfach verknüpft sind, während die entsprechenden Ge-Atome in 2 a nur dreifach gebunden sind. Die Bindungen innerhalb des Dreirings Ge4 bis Ge6 in 3 a wurden als Dreizentren-Zweielektronen-Bindung beschrieben, [22] und mit 3.254-3.264 sind sie deutlich länger als ihre Gegenstücke in 2 a. Damit können die Bindungsverhältnisse in 2 a sogar noch zutreffender als Dreizentren-Zweielektronen-Bindung beschrieben werden.…”