[(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.

Two new alkali metal monoalkyl-bisamido magnesiates, the potassium compound [KMg(TMP) 2 n Bu] and its sodium congener [NaMg(TMP) 2 n Bu] have been synthesised in crystalline form (TMP ¼ 2,2,6,6tetramethylpiperidide). Devoid of solvating ligands and possessing excellent solubility in hydrocarbon solvents, these compounds open up a new gateway for the synthesis of inverse crowns. X-ray crystallography established that [KMg(TMP) 2 n Bu] exists in three polymorphic forms, namely a helical polymer with an infinite KNMgN chain, a hexamer with a 24-atom (KNMgN) 6 ring having endo-disposed alkyl substituents, and a tetramer with a 16-atom (KNMgN) 4 ring also having endo-disposed alkyl substituents. Proving their validity as pre-inverse-crowns, both magnesiates react with benzene and toluene to generate known inverse crowns in syntheses much improved from the original, supporting the idea that the metallations take place via a template effect. [KMg(TMP) 2 n Bu] reacts with naphthalene to generate the new inverse crown [KMg(TMP) 2 (2-C 10 H 7 )] 6 , the molecular structure of which shows a 24-atom (KNMgN) 6 host ring with six naphthalene guest anions regioselectively magnesiated at the 2-position. An alternative unprecedented 1,4-dimagnesiation of naphthalene was accomplished via [NaMg(TMP) 2 n Bu] and its NaTMP co-complex "[NaMg(TMP) 2 n Bu]$NaTMP", manifested in [{Na 4 Mg 2 (TMP) 4 (2,2,6trimethyl-1,2,3,4-tetrahydropyridide) 2 }(1,4-C 10 H 6 )]. Adding to its novelty, this 12-atom (NaNNaNMgN) 2 inverse crown structure contains two demethylated TMP ligands as well as four intact ones. Reactivity studiesshow that the naphthalen-ide and -di-ide inverse crowns can be regioselectively iodinated to 2-iodo and 1,4-diiodonaphthalene respectively.Scheme 1 Synthesis of inverse crown complexes 1a/b and 2a/b (for a R ¼ H; for b R ¼ Me).

As the aluminate base [LiAl(TMP)(2)(iBu)(2)] 1 displays halogen tolerance towards substituted aromatics, 4-halo-anisoles have been ortho-aluminated and electrophilically quenched to form synthetically useful multi-heterohalogenated anisoles, with the Al intermediates along the route structurally defined.

The reduction of mononitro and dinitro aromatic compounds to their aniline analogues using microwave-assisted transfer hydrogenation has been demonstrated. The optimised conditions used, with some examples, are described herein.