Synthesis and reactivity of a terminal aluminium–imide bond

Abstract

The reaction of the potassium aluminyl K[Al(NONDipp)] (NONDipp = [O(SiMe2NDipp)2]2-, Dipp = 2,6-iPr2C6H3) with an organic azide generates the aluminium imide complex, K[Al(NONDipp)(NMes)] (Mes = mesityl = 2,4,6-Me3C6H2). DFT calculations indicate the Al-Nimide interaction is polarized but has appreciable multiple-bond character. This is demonstrated experimentally by the reaction with carbon dioxide, giving a rare example of a main group carbamate dianion via a [2+2] cycloaddition reaction.