One silicon atom of bis(silylene) functions as a selective Lewis base under adduct formation with a Lewis acid

Roesky, Herbert W.; Ding, Yi; Nazish, Mohd; Ruth, Paul Niklas; Herbst‐Irmer, Regine

doi:10.1039/d3dt00811h

Dalton Trans.

2023

DOI: 10.1039/d3dt00811h

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One silicon atom of bis(silylene) functions as a selective Lewis base under adduct formation with a Lewis acid

Herbert W. Roesky

Yi Ding

Mohd Nazish

et al.

Abstract: Herein, we describe the facile and selective one-pot synthetic route to silylene-aluminum and silylene-gallium adducts. Reduction of silylene LSiCl (L = PhC(NtBu)2) with KC8 in the presence of bulky and...

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2024

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Cited by 2 publications

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Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character

Saddington,

Dong,

Yao

et al. 2024

Angewandte Chemie

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The suitability of electron‐rich bis‐silylenes, specifically the neutral chelating [SiII(Xant)SiII] ligand (SiII = PhC(NtBu)2Si, Xant = 9,9dimethylxanthene) and the anionic [SiII(NAcrid)SiII)]‒ pincer ligand (NAcrid = 2,7,9,9‐tetramethylacridane), has been successfully probed to stabilize monovalent bis‐silylene‐supported aluminium complexes (aluminylenes). At first, the unprecedented aluminium(III) iodide precursors [SiII(Xant)SiII]AlI2+ I‒ 1 and [SiII(NAcrid)SiII)]AlI2 2 were synthesized using AlI3 and [SiII(Xant)SiII] or [SiII(NAcrid)SiII)]Li(OEt2)], respectively, and structurally characterized. While reduction of 1 with KC8 led merely to unidentified products, the dehalogenation of 2 afforded the dimer of the desired {[SiII(NAcrid)SiII)]Al:} aluminylene with a four‐membered SiIV2AlIII2 ring. Remarkably, the proposed aluminylene intermediates [SiII(Xant)SiII]AlII and {[SiII(NAcrid)SiII)]Al:} could be produced through reduction of 1 and 2 with Collman’s reagent, K2Fe(CO)4, and trapped as AlI:→Fe(CO)4 complexes 5 and 6 , respectively. While6is stable in solution,5loses one CO ligand in solution to afford the silylene‐ and aluminylene‐coordinated iron(0) complex7. The electronic structures of the novel compounds were investigated by Density Functional Theory calculations.

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Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character

Saddington,

Dong,

Yao

et al. 2024

Angewandte Chemie

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Isolation and Diverse Reactivity of an Unsymmetrical 1,2-Bis(silylene)-Stabilized Pentacarbonyl Chromium(0) Species

Fan,

Wang,

Shi

et al. 2024

Inorg. Chem.

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One silicon atom of bis(silylene) functions as a selective Lewis base under adduct formation with a Lewis acid

Abstract: Herein, we describe the facile and selective one-pot synthetic route to silylene-aluminum and silylene-gallium adducts. Reduction of silylene LSiCl (L = PhC(NtBu)2) with KC8 in the presence of bulky and...

Cited by 2 publications

References 49 publications

Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character

Bis‐Silylene‐Supported Aluminium Atoms with Aluminylene and Alane Character

Isolation and Diverse Reactivity of an Unsymmetrical 1,2-Bis(silylene)-Stabilized Pentacarbonyl Chromium(0) Species

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