Abstract
AbstractThe synthesis and characterization of the first bis‐N‐heterocyclic carbene stabilized monomeric silicon disulfide (bis‐NHC)SiS2 2 (bis‐NHC=H2C[{NC(H)C(H)N(Dipp)}C:]2, Dipp=2,6‐iPr2C6H3) is reported. Compound 2 is prepared in 89 % yield from the reaction of the zero‐valent silicon complex (′silylone′) 1 [(bis‐NHC)Si] with elemental sulfur. Compound 2 can react with GaCl3 in acetonitrile to give the corresponding (bis‐NHC)Si(S)S→GaCl3 Lewis acid–base adduct 3 in 91 % yield. Compound 3 is also accessible through the reaction of the unprecedented silylone‐GaCl3 adduct [(bis‐NHC)Si→GaCl3] 4 with elemental sulfur. Compounds 2, 3, and 4 could be isolated and characterized by elemental analyses, HR‐MS, IR, 13C‐ and 29Si‐NMR spectroscopy. The structures of 3 and 4 could be determined by single‐crystal X‐ray diffraction analyses. DFT‐derived bonding analyses of 2 and 3 exhibited highly polar SiS bonds with moderate pπ–pπ bonding character.
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