Issue 16, 2019

Site-selective functionalization of Si6R6 siliconoids

Abstract

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 Si6R6 siliconoid at a different vertex than in the previously reported isomeric 4-lithiated derivative (R = 2,4,6-iPr3C6H2). In order to enable an intuitive distinction of the vertices of the global minimum Si6R6 scaffold (which can be considered the silicon analogue of benzene in terms of thermodynamic stability), we introduce a novel nomenclature in analogy to the orthometapara nomenclature of disubstituted benzenes. By treatment of the 2-lithiated Si6 cluster with Me3SiCl, SiCl4 H3B·SMe2, (Me2N)2PCl as well as with carboxylic acid chlorides RCOCl (R = tBu, Ph) various 2-functionalized Si6 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.

Graphical abstract: Site-selective functionalization of Si6R6 siliconoids

Supplementary files

Article information

Article type
Edge Article
Submitted
14 Dec 2018
Accepted
07 Mar 2019
First published
14 Mar 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 4523-4530

Site-selective functionalization of Si6R6 siliconoids

Y. Heider, N. E. Poitiers, P. Willmes, K. I. Leszczyńska, V. Huch and D. Scheschkewitz, Chem. Sci., 2019, 10, 4523 DOI: 10.1039/C8SC05591B

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