Potassium Aluminyl Promoted Carbonylation of Ethene

The potassium aluminyl [K{Al(NON(Dipp))}](2) ([NON(Dipp)](2−)=[O{SiMe(2)NDipp}(2)](2−), Dipp=2,6‐iPr(2)C(6)H(3)) activates ethene towards carbonylation with CO under mild conditions. An isolated bis‐aluminacyclopropane compound reacted with CO via carbonylation of an Al−C bond, followed by an intramolecular hydrogen shift to form K(2)[Al(NON(Dipp))(μ‐CH(2)CH=CO‐1κ(2) C (1,3)‐2κO)Al(NON(Dipp))Et]. Restricting the chemistry to a mono‐aluminium system allowed isolation of [Al(NON(Dipp))(CH(2)CH(2)CO‐κ(2) C (1,3))](−), which undergoes thermal isomerisation to form the [Al(NON(Dipp))(CH(2)CH=CHO‐κ(2) C,O)](−) anion. DFT calculations highlight the stabilising influence of incorporated benzene at multiple steps in the reaction pathways.