β‐Ketoimine ligands stabilize zinc compounds: The dimeric zinc alkylperoxide [{(LL)ZnOOEt}2] (where LL=HC{(CMe)(2,6‐iPr2C6H3N)}2) has been prepared and structurally characterized (see picture, Zn green, N blue, O red, C gray). This compound, which is formed by the insertion of dioxygen into the ZnEt bond, is very active in the epoxidation of enones.

Despite the fact that extensive research has been carried out, the oxygenation of alkyl magnesium species still remains a highly unexplored research area and significant uncertainties concerning the mechanism of these reactions and the composition of the resulting products persist. This case study compares the viability of the controlled oxygenation of alkylmagnesium complexes supported by β-diketiminates. The structural tracking of the reactivity of (N,N)MgR-type complexes towards O at low temperature showed that their oxygenation led exclusively to the formation of magnesium alkylperoxides (N,N)MgOOR. The results also highlight significant differences in the stability of the resulting alkylperoxides in solution and demonstrate that [(BDI)Mg(μ-η :η -OOBn)] (in which BDI=[(ArNCMe) CH] and Ar=C H iPr -2,6) can be easily transformed to the corresponding magnesium alkoxide [(BDI)MgOBn] at ambient temperature, whilst [( BDI)Mg(μ-OOtBu)] (in which BDI=[(ArNCMe) CH] and Ar=C H F -2,4,6) is stable under similar conditions. The observed selective oxygenation of (N,N)MgR-type complexes to the corresponding (N,N)MgOOR alkylperoxides strongly contradicts the widely accepted radical-chain mechanism for the oxygenation of the main-group-metal alkyls. Furthermore, either the observed transformation of the alkylperoxide [(BDI)MgOOBn] to the alkoxide [(BDI)MgOBn] as well as the formation of an intractable mixture of products in the control reaction between the alkylperoxide [( BDI)MgOOtBu] and the parent alkylmagnesium [( BDI)MgtBu] complex are not in line with the common wisdom that magnesium alkoxide complexes' formation results from the metathesis reaction between MgOOR and Mg-R species. In addition, a high catalytic activity of well-defined magnesium alkylperoxides, in combination with tert-butyl hydroperoxide (TBHP) as an oxygen source, in the epoxidation of trans-chalcone is presented.

Summary: The isolation and structural characterization of a methylaluminium(bisphenoxide)‐ε‐caprolactone complex is reported. While the three‐coordinate methylaluminium complex was found not to catalyze the polymerization of ε‐caprolactone, its oxygenation led to the formation of an aluminium methoxide compound, which appeared to be a very good initiator. The relative propensity of the AlX bonds for monomer insertion in the initial step of polymerization is also discussed.Structure of the methylaluminium(bisphenoxide)‐ε‐caprolactone complex reported here.imageStructure of the methylaluminium(bisphenoxide)‐ε‐caprolactone complex reported here.

The epoxidation of enones by zinc alkylperoxides is a challenging task receiving considerable attention in contemporary research; however, until now no welldefined zinc alkylperoxide based systems have been described. Here, a new catalytic method of epoxidation of enones in the presence of zinc alkylperoxides supported by N,N-bidentate ligands and tert-butyl hydroperoxide is reported. A new dimeric zinc alkylperoxide complex supported by an aminotroponiminate ligand is also presented. The studied catalytic systems show high activity in the epoxidation of trans-chalcone, and in the case of a chiral catalyst with the (S,S)-N,N′-bis(1-phenylethyl)aminotroponiminate ligand a moderate enantioselectivity was achieved.

β‐Ketoiminliganden stabilisieren Zinkkomplexe: Das dimere Zinkalkylperoxid [{(LL)ZnOOEt}2] (LL=HC{(CMe)(2,6‐iPr2C6H3N)}2) wurde isoliert und strukturell charakterisiert (siehe Bild, Zn grün, N blau, O rot, C grau). Der Komplex, der durch Insertion von Disauerstoff in die Zn‐Et‐Bindung gebildet wird, ist hoch aktiv in der Epoxidierung von Enonen.