Carbon-chalcogen bond formation initiated by [Al(NON Dipp )(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 Dipp )(S)] (NON Dipp = [O(SiMe 2 NDipp) 2 ] 2- , Dipp = 2,6- i Pr 2 C 6 H 3 ), completing the series of [Al(NON Dipp )(E)] - anions containing Al-E{16} multiple bonds (E{16} = O, S, Se, Te), was accessed via desulfurisation of K[Al(NON Dipp )(S 4 )] 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 Dipp )(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 Dipp )(E)] (E = S, Se) with CO 2 afforded K[Al(NON Dipp )(κ 2 E , O -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 2 E , O -EC{O}Ph 2 ] 2- . In contrast, when K[Al(NON Dipp )(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 2 O , O -thio- and κ 2 O , O -seleno-bis(phenylmethanolate) ligands, which were exclusively isolated as the cis -stereoisomers. The mechanisms of these cycloaddition reactions were investigated using DFT methods.