A seven‐membered N,N′‐heterocyclic potassium alumanyl nucleophile is introduced and utilised in the metathetical synthesis of Mg−Al and Ca−Al bonded derivatives. Both species have been characterised by experimental and theoretical means, allowing a rationalisation of the greater reactivity of the heavier group 2 species implied by an initial assay of their reactivity.

Copper‐alumanyl complexes, [LCu‐Al(SiNDipp)], where L=carbene=NHCiPr (N,N′‐diisopropyl‐4,5‐dimethyl‐2‐ylidene) and Me2CAAC (1‐(2,6‐diisopropylphenyl)‐3,3,5,5‐tetramethyl‐pyrrolidin‐2‐ylidene) and featuring unsupported Al−Cu bonds, have been prepared. Divergent reactivity observed with carbodiimides and CO2 implies an ambiphilicity in the Cu–Al interaction that is dependent on the identity of the carbene co‐ligand.

Density functional theory was used to investigate the protodeauration of organogold compounds, a process which is thought to be the final step in the gold-catalyzed nucleophilic addition to activated π bonds wherein a proton is added and the gold catalyst is regenerated. In this context, we have studied two important factors which control the effectiveness of this transformation. We find that the nature of the alkenyl group in PMe3Au­(alkenyl) affects the reaction barrier through the strength of the Au–C bond; the stronger the Au–C bond, the higher the activation energy. This, in turn, is determined by the π-accepting/donating ability of the substituents on the alkenyl group. We theoretically confirm that, for protodeauration, the reaction should be rapid when π-donating groups are present. In contrast, when π-accepting substituents are present, the intermediate gold complexes may be stable enough to be isolated experimentally. The second important factor controlling the reaction is the nature of the phosphine ligands. We theoretically confirm that electron-rich ligands such as PMe3 or PPh3 accelerate the reaction. We find that this is due to the strong electron-donating nature of these ligands, which strengthens the Au–P bond in the final product and thus provides a thermodynamic driving force for the reaction. Also, it is shown how the protodeauration is affected by the number of molecules solvating the proton. The protodeauration mechanism of some other organogold compounds such as gold–alkyl, gold–alkynyl, and gold–allyl species was investigated as well. The findings of this study can be used to design more effective systems for transformations of organogold compounds.

[K{Al(NONDipp)}]2 (NONDipp=[O(SiMe2NDipp)2]2−, Dipp=2,6‐iPr2C6H3) reacts with CS2 to afford the trithiocarbonate species [K(OEt2)][Al(NONDipp)(CS3)] 1 or the ethenetetrathiolate complex, [K{Al(NONDipp)(S2C)}]2 [3]2. The dimeric alumoxane [K{Al(NONDipp)(O)}]2 reacts with carbon monoxide to afford the oxygen analogue of 3, [K{Al(NONDipp)(O2C)}]2 [4]2 containing the hitherto unknown ethenetetraolate ligand, [C2O4]4−.

Through a dramatic advance in the coordination chemistry of the zinc-hydride bond, we describe the trajectory for the approach of this bond to transition metals. The dynamic reaction coordinate was interrogated through analysis of a series of solid state structures and is one in which the TM-H-Zn angle becomes increasingly acute as the TM-Zn distance decreases. Parallels may be drawn with the oxidative addition of boron-hydrogen and silicon-hydrogen bonds to transition metal centers.