Abstract
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.