Annulated 1,4-Disilabenzene-1,4-diide and Dihydrogen Splitting

• DOI: 10.1021/jacs.4c12127
• Publication Date: 2024-10-23T07:10:37Z
• Authors: Falk Ebeler; Yury V. Vishnevskiy; Beate Neumann; Hans-Georg Stammler; Dariusz W. Szczep...; Rajendra S. Ghadwal

The isolation of silicon analogues of phenyl anions such as (C6H5)- and (C6H4)2- is challenging owing to their extremely high reactivity associated with their silylene character and weak C-Si π-interaction. Herein, we report the first annulated 1,4-disilabenzene-1,4-diide compound [(ADC)Si]2 (5) based on anionic dicarbene (ADC) scaffolds (ADC = PhC{N(Dipp)C}2; Dipp = 2,6-iPr2C6H3) as a green-yellow crystalline solid. Compound 5 is prepared by KC8 reduction of the Si(IV) chloride [(ADC)SiCl3]2 (3) or the cyclic bis-chlorosilylene [(ADC)SiCl]2 (4), which are also prepared for the first time. 5 is a neutral molecule, and each of the two-coordinated Si(I) atoms has a lone pair and an unpaired electron. Experimental and theoretical data indicate delocalization of the silicon unpaired electrons, resulting in a 6π-electron C4Si2 ring in 5. The diradical character (y) for 5 amounts to 15%. At room temperature, 5 readily reacts with dihydrogen (H2) to form the elusive bis-hydridosilylenes [(ADC)SiH]2 (Z)-6 and (E)-6. The [4 + 2]-cycloaddition of 5 and PhC≡CPh in yielding the barrelene-type bis-silylene [(ADC)SiCPh]2 (7) emphasizes the diradical reactivity of 5. With elemental sulfur, 5 results in the S2- and S3-bridged silathione derivatives [(ADC)Si(S)]2(μ-S2) (8a) and [(ADC)Si(S)]2(μ-S3) (8b). Moreover, the treatment of 5 with Fe2(CO)9 affords the Fe(0) complex [(ADC)Si(Fe(CO)4)]2(μ-CO) (9), in which each silicon atom serves as a two-electron σ-donor ligand and shares one electron with the bridging CO unit to form two Si-C bonds. The molecular structures of all compounds have been established by X-ray diffraction, and representative compounds have been analyzed by quantum chemical calculations.