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• W4226419333 endingPage "4646" @default.
• W4226419333 startingPage "4635" @default.
• W4226419333 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(NONDipp)(S)] (NONDipp = [O(SiMe2NDipp)2]2-, Dipp = 2,6-iPr2C6H3), completing the series of [Al(NONDipp)(E)]- anions containing Al-E{16} multiple bonds (E{16} = O, S, Se, Te), was accessed via desulfurisation of K[Al(NONDipp)(S4)] 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(NONDipp)(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(NONDipp)(E)] (E = S, Se) with CO2 afforded K[Al(NONDipp)(κ2E,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, [κ2E,O-EC{O}Ph2]2-. In contrast, when K[Al(NONDipp)(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 κ2O,O-thio- and κ2O,O-seleno-bis(phenylmethanolate) ligands, which were exclusively isolated as the cis-stereoisomers. The mechanisms of these cycloaddition reactions were investigated using DFT methods." @default.
• W4226419333 created "2022-05-05" @default.
• W4226419333 creator A5005139483 @default.
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• W4226419333 creator A5082402719 @default.
• W4226419333 date "2022-01-01" @default.
• W4226419333 modified "2023-10-14" @default.
• W4226419333 title "Carbon–chalcogen bond formation initiated by [Al(NON^Dipp)(E)]⁻anions containing Al–E{16} (E{16} = S, Se) multiple bonds" @default.
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• W4226419333 doi "https://doi.org/10.1039/d2sc01064j" @default.
• W4226419333 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/35656129" @default.
• W4226419333 hasPublicationYear "2022" @default.
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