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. 2023 Sep 28;14(44):12477-12483.
doi: 10.1039/d3sc02709k. eCollection 2023 Nov 15.

Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb) and ECl{N(SiMe3)2} (E = Ge, Sn)

Javier A Cabeza  1 , Javier F Reynes  1 , Felipe García  1   2 , Pablo García-Álvarez  1 , Rubén García-Soriano  1
Affiliations

Fast and scalable solvent-free access to Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge, Sn, Pb) and ECl{N(SiMe3)2} (E = Ge, Sn)

Javier A Cabeza et al. Chem Sci. .

Abstract

Iconic Lappert's heavier tetrylenes E{N(SiMe3)2}2 (E = Ge (1), Sn (2), Pb (3)) have been efficiently prepared from GeCl2·(1,4-dioxane), SnCl2 or PbCl2 and Li{N(SiMe3)2} via a completely solvent-free one-pot mechanochemical route followed by sublimation. This fast, high-yielding and scalable approach (2 has been prepared in a 100 mmol scale), which involves a small environmental footprint, represents a remarkable improvement over any synthetic route reported over the last five decades, being a so far rare example of the use of mechanochemistry in the realm of main group chemistry. This solventless route has been successfully extended to the preparation of other heavier tetrylenes, such as ECl{N(SiMe3)2} (E = Ge (4), Sn (5)).

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Conflict of interest statement

There are no conflicts to declare.

Figures

Fig. 1
Fig. 1. Conventional solution-based (ref. 24c) vs. mechanochemical syntheses (this work) for compounds 1–3.
Fig. 2
Fig. 2. Side-by-side comparison of the 10 and 100 mmol scale reactions (left and right, respectively) for the synthesis of Sn{N(SiMe3)2}2 (2). The inserts display the crude product obtained in 10 mL and the 250 mL stainless steel jars, and the resulting isolated product stored in a 20 mL vial and a 100 mL Schlenk tube for the small and large scales, respectively. See ESI for expanded NMRs.
Scheme 1
Scheme 1. Mechanochemical reactions of homoleptic E{N(SiMe3)2}2 (E = Ge (1), Sn (2) and Pb (3)) with the corresponding tetrel dihalide to produce heteroleptic ECl{N(SiMe3)2}2 (E = Ge (4) and Sn (5)).
See this image and copyright information in PMC

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