Diverse Multinuclear Alkali Metallated (Li, Na, K, Rb, Cs) Family of the 1,3,5-tris-2-aminopyridyl-2,4,6-triethylbenzene Framework.

Literature on Group One organoelement chemistry is dominated by lithium, though sodium and potassium also feature prominently, whereas rubidium and caesium are rarely mentioned. With recent breakthroughs hinting that organoelement compounds of these two heavier metals can perform better than their lighter congeners in particular applications, important advantages could be missed unless complete sets of alkali metals are included in studies. Here, we report the synthesis and characterisation of a complete set of multi-alkali-metallated molecular compounds of the 1,3,5-tris[(4,6-dimethylpyridin-2-yl)aminomethyl]-2,4,6-triethylbenzene framework.

Application of Bis(amido)alkyl Magnesiates toward the Synthesis of Molecular Rubidium and Cesium Hydrido-magnesiates.

Rubidium and cesium are the least studied naturally occurring s-block metals in organometallic chemistry but are in plentiful supply from a sustainability viewpoint as highlighted in the periodic table of natural elements published by the European Chemical Society. This underdevelopment reflects the phenomenal success of organometallic compounds of lithium, sodium, and potassium, but interest in heavier congeners has started to grow. Here, the synthesis and structures of rubidium and cesium bis(amido)alkyl magnesiates [(AM)MgN'alkyl], where N' is the simple heteroamide N(SiMe)(Dipp), and alkyl is Bu or CHSiMe, are reported.

Synthesis, characterisation, and catalytic application of a soluble molecular carrier of sodium hydride activated by a substituted 4-(dimethylamino)pyridine.

Recently main group compounds have stepped into the territory of precious transition metal compounds with respect to utility in the homogeneous catalysis of fundamentally important organic transformations. Inspired by the need to promote more sustainability in chemistry because of their greater abundance in nature, this change of direction is surprising since main group metals generally do not possess the same breadth of reactivity as precious transition metals. Here, we introduce the dihydropyridylsodium compound, Na-1,2-tBu-DH(DMAP), and its monomeric variant [Na-1,2-tBu-DH(DMAP)]·MeTREN, and demonstrate their effectiveness in transfer hydrogenation catalysis of the representative alkene 1,1-diphenylethylene to the alkane 1,1-diphenylethane using 1,4-cyclohexadiene as hydrogen source [DMAP = 4-dimethylaminopyridine; MeTREN = tris(N,N-dimethyl-2-aminoethyl)amine].

Modification of a Common β-diketiminate NacNac Framework via Sequential Lithiation and Small Molecule Insertion.

A widely utilised class of ligands in synthesis and catalysis, β-diketiminate (BDI) or NacNac compounds were initially considered innocent in the sense that they remained intact in all their applications. That changed when the γ-C-H unit of their NCCCN backbone was found to engage in reactions with electrophiles. Here, we show that this special reactivity can be used advantageously to prepare tripodal modifications of the common NacNac ligand derived from 2,6-diisopropylphenyl-β-methyldiketimine [NacNacH (Me, Dipp)].

Isolable rubidium and caesium derivatives of common organic carbonyl compounds.

Light alkali metal (Li, Na, K) amides have a long history of synthetic utility, but heavier (Rb, Cs) congeners have barely been studied. This study reveals remarkable structurally complex outcomes of reacting AM(HMDS) (AM = Rb, Cs; HMDS = hexamethyldisilazide) with benzaldehyde and acetophenone. Though complicated, reactions give a diversity of eye-catching isolated products, an enolate with a hexagonal prismatic network, two dienolates with distinct extended ladder motifs, and two β-imino-alkoxides comprising zig-zag chains of metal-oxygen bonds in infinite cages.