Synthesis and Characterization of a Metalloid Ge 6 Cluster with Bulky Amide Ligands.
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| Title: | Synthesis and Characterization of a Metalloid Ge 6 Cluster with Bulky Amide Ligands. |
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| Authors: | Liu, Jingjing1,2 (AUTHOR), Liu, Xiaoting1,2 (AUTHOR), Zhang, Bin1,3 (AUTHOR), Ji, Caiting1 (AUTHOR), Sun, Xiaohui1,2 (AUTHOR), Wang, Wenyuan2,3 (AUTHOR) wangwy@nwu.edu.cn, Bo, Xiaoxu3 (AUTHOR) boxxsci@163.com |
| Source: | Materials (1996-1944). Jun2026, Vol. 19 Issue 12, p2516. 12p. |
| Subjects: | Metal clusters, Ligands (Chemistry), X-ray diffraction, Molecular structure, Germylenes, Electron delocalization |
| Abstract: | This article details the synthesis and structural characterization of a new metalloid germanium cluster 3 with bulky amide ligands. The cluster features a Ge6 core stabilized by four -N(SitBuMe2)2 ligands and was obtained via reduction of the amido trichlorogermane 2 using potassium chips in toluene. Single-crystal X-ray diffraction analysis revealed that the Ge6 core adopts a butterfly-shaped geometry with a Ge-Ge dumbbell unit, which contains two unsubstituted germanium atoms exhibiting prominent lone-pair characteristics. The Ge6 core can also be classified as a nido cluster, with a cluster-bonding-electron count of 16, perfectly satisfying the 2n + 4 electron-counting rule. Combining the structural features of this nido cluster with the bond length distribution in the folded four-membered ring suggests that the Ge4 ring features a certain degree of electron delocalization. Additionally, two bis(amido)-substituted germylenes (4 and 6) were isolated and structurally characterized. They exhibit analogous structural features, with each germanium center adopting a two-coordinate V-shaped configuration, the Ge–N bond lengths being very similar, and the nitrogen atoms adopting a planar triangular geometry. Notably, compound 6, bearing bulkier -N(SiiPr3)2 substituents, exhibits a significantly larger N-Ge-N bond angle (120.58°) compared to the corresponding value of 113.54° observed for compound 4 with -N(SitBuMe2)2 substituents. This clearly demonstrates that the steric bulk of the substituents exerts a remarkable influence on the molecular geometry and σ-donor ability of the lone pairs on germanium centers. [ABSTRACT FROM AUTHOR] |
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| Database: | Engineering Source |
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| Abstract: | This article details the synthesis and structural characterization of a new metalloid germanium cluster 3 with bulky amide ligands. The cluster features a Ge6 core stabilized by four -N(SitBuMe2)2 ligands and was obtained via reduction of the amido trichlorogermane 2 using potassium chips in toluene. Single-crystal X-ray diffraction analysis revealed that the Ge6 core adopts a butterfly-shaped geometry with a Ge-Ge dumbbell unit, which contains two unsubstituted germanium atoms exhibiting prominent lone-pair characteristics. The Ge6 core can also be classified as a nido cluster, with a cluster-bonding-electron count of 16, perfectly satisfying the 2n + 4 electron-counting rule. Combining the structural features of this nido cluster with the bond length distribution in the folded four-membered ring suggests that the Ge4 ring features a certain degree of electron delocalization. Additionally, two bis(amido)-substituted germylenes (4 and 6) were isolated and structurally characterized. They exhibit analogous structural features, with each germanium center adopting a two-coordinate V-shaped configuration, the Ge–N bond lengths being very similar, and the nitrogen atoms adopting a planar triangular geometry. Notably, compound 6, bearing bulkier -N(SiiPr3)2 substituents, exhibits a significantly larger N-Ge-N bond angle (120.58°) compared to the corresponding value of 113.54° observed for compound 4 with -N(SitBuMe2)2 substituents. This clearly demonstrates that the steric bulk of the substituents exerts a remarkable influence on the molecular geometry and σ-donor ability of the lone pairs on germanium centers. [ABSTRACT FROM AUTHOR] |
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| ISSN: | 19961944 |
| DOI: | 10.3390/ma19122516 |
