The element lithium has been discovered 200 years ago. Due to its unique properties it has emerged to play a vital role in industry, esp. for energy storage, and lithium‐based products and processes support sustainable technological developments. In addition to the many uses of lithium in its inorganic forms, lithium has a rich organometallic chemistry. The development of organometallic chemistry has been hindered by synthetic problems from the start. When Wilhelm Schlenk developed the basic principles to handle and synthesize air‐ and moisture‐sensitive compounds, the road was open to further developments. After more information was available about the stability and solubility of such compounds, they started to play an essential role in other fields of chemistry as alkyl or aryl transfer reagents.

The molecular engines that drive enhanced magnesiations are unveiled through structural elucidation of a 2,2,6,6‐tetramethylpiperidide (TMP) Hauser base and its turbo model (see structure; Mg green, Li violet, C purple, O red, N blue, Cl yellow).

Check M(etal)ate: The chessboard and the figures represent a special reaction in which different low‐polarity metals can metalate arenes directly when they are brought into the right position. In a combination of queen (sodium) and knight (chromium or iron), it is possible for the knight (usually the weaker piece) to make a direct deadly hit on the king (benzene) in this game of elemental chess. magnified image

[(Trimethylsilyl)methyl]sodium [NaCH₂SiMe₃] (1) was prepared by a metathesis reaction of [(trimethylsilyl)methyl]lithium [LiCH₂SiMe₃] with sodium tert‐butoxide in n‐hexane. Polydentate donors such as N,N,N′,N′‐tetramethylethylenediamine (TMEDA) and N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) form n‐hexane‐soluble complexes of 1 and the potassium congener [KCH₂SiMe₃] (2). The crystal structures of the polymers [(TMEDA)NaCH₂SiMe₃] (1a) and [(PMDETA)KCH₂SiMe₃] (2a) were determined as infinite helical chains exhibiting 3₁ or 3₂ screw‐axis symmetry. Compound 2b was obtained as the donor‐deficient heterocubane pseudotetramer [(TMEDA)₃(KCH₂SiMe₃)₄], with intermolecular interactions of the TMEDA‐uncoordinated potassium atom with a peripheral methyl group of a neighbouring tetramer to form infinite chains. The relatively easy accessibility and stability should make these (trimethylsilyl)methyl compounds of sodium and potassium valuable starting points for further exploration of the chemistry of these common‐utility heavier alkali metals.