Affiliation:
1. Department of Chemistry: Metalorganics and Inorganic Materials Technische Universität Berlin Strasse des 17. Juni 115, Sekr. C2 10623 Berlin Germany
2. State Key Laboratory of Physical Chemistry of Solid Surfaces Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry College of Chemistry and Chemical Engineering Xiamen University 361005 Xiamen China
3. School of Science and Engineering Chinese University of Hong Kong, Shenzhen No. 2001 Longxiang Blvd., Longgang Dist. Shenzhen Guangdong 518172 China
Abstract
AbstractThe suitability of electron‐rich bis‐silylenes, specifically the neutral chelating [SiII(Xant)SiII] ligand (SiII=PhC(NtBu)2Si, Xant=9,9‐dimethylxanthene) 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 reaction of 1 and 2 with Collman's reagent, K2Fe(CO)4, and trapped as AlI:→Fe(CO)4 complexes 5 and 6, respectively. While 6 is stable in solution, 5 loses one CO ligand in solution to afford the silylene‐ and aluminylene‐coordinated iron(0) complex 7 from an intramolecular substitution reaction. The electronic structures of the novel compounds were investigated by Density Functional Theory calculations.