Site-selective functionalization of Si6R6 siliconoidsElectronic supplementary information (ESI) available: CCDC 1877380 (5a), 1877381 (5b), 1877378 (4Li), 1877379 (6a), 1877382 (6c), 1877383 (6f). For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c8sc05591b
The recent progress in the synthesis of partially substituted neutral silicon clusters (siliconoids) revealed unique structures and electronic anisotropies that are reminiscent of bulk and nano surfaces of silicon. Here, we report the selective 2-lithiation of the global minimum Si 6 R 6 siliconoid...
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| Main Authors: | , , , , , |
|---|---|
| Format: | Journal Article |
| Published: |
17-04-2019
|
| Online Access: | Get full text |
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| Summary: | The recent progress in the synthesis of partially substituted neutral silicon clusters (siliconoids) revealed unique structures and electronic anisotropies that are reminiscent of bulk and nano surfaces of silicon. Here, we report the selective 2-lithiation of the global minimum Si
6
R
6
siliconoid at a different vertex than in the previously reported isomeric 4-lithiated derivative (R = 2,4,6-
i
Pr
3
C
6
H
2
). In order to enable an intuitive distinction of the vertices of the global minimum Si
6
R
6
scaffold (which can be considered the silicon analogue of benzene in terms of thermodynamic stability), we introduce a novel nomenclature in analogy to the
ortho
-
meta
-
para
nomenclature of disubstituted benzenes. By treatment of the 2-lithiated Si
6
cluster with Me
3
SiCl, SiCl
4
H
3
B·SMe
2
, (Me
2
N)
2
PCl as well as with carboxylic acid chlorides RCOCl (R =
t
Bu, Ph) various 2-functionalized Si
6
clusters were obtained and characterized in solution and - in most cases - the solid state. The structural and spectroscopic effect of the position of the newly introduced functional group is discussed by comparison to the corresponding 4-functionalized derivatives.
The recent progress in the synthesis of partially substituted neutral silicon clusters (siliconoids) revealed unique structures and electronic anisotropies that are reminiscent of bulk and nano surfaces of silicon. |
|---|---|
| Bibliography: | 1877381 1877380 1877383 1877382 ( ) 6a 10.1039/c8sc05591b 5a 1877378 5b 6c 1877379 6f 4Li For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: CCDC |
| ISSN: | 2041-6520 2041-6539 |
| DOI: | 10.1039/c8sc05591b |