Carbon-chalcogen bond formation initiated by [Al(NON)(E)] anions containing Al-E{16} (E{16} = S, Se) multiple bonds.

Multiply-bonded main group metal compounds are of interest as a new class of reactive species able to activate and functionalize a wide range of substrates. The aluminium sulfido compound K[Al(NON)(S)] (NON = [O(SiMeNDipp)], Dipp = 2,6-PrCH), completing the series of [Al(NON)(E)] anions containing Al-E{16} multiple bonds (E{16} = O, S, Se, Te), was accessed desulfurisation of K[Al(NON)(S)] using triphenylphosphane. The crystal structure showed a tetrameric aggregate joined by multiple K⋯S and K⋯π(arene) interactions that were disrupted by the addition of 2.2.2-cryptand to form the separated ion pair, [K(2.2.2-crypt)][Al(NON)(S)]. Analysis of the anion using density functional theory (DFT) confirmed multiple-bond character in the Al-S group. The reaction of the sulfido and selenido anions K[Al(NON)(E)] (E = S, Se) with CO afforded K[Al(NON)(κ ,-EC{O}O)] containing the thio- and seleno-carbonate groups respectively, consistent with a [2 + 2]-cycloaddition reaction and C-E bond formation. An analogous cycloaddition reaction took place with benzophenone affording compounds containing the diphenylsulfido- and diphenylselenido-methanolate ligands, [κ ,-EC{O}Ph]. In contrast, when K[Al(NON)(E)] (E = S, Se) was reacted with benzaldehyde, two equivalents of substrate were incorporated into the product accompanied by formation of a second C-E bond and complete cleavage of the Al-E{16} bonds. The products contained the hitherto unknown κ ,-thio- and κ ,-seleno-bis(phenylmethanolate) ligands, which were exclusively isolated as the -stereoisomers. The mechanisms of these cycloaddition reactions were investigated using DFT methods.