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From Silylone to an Isolable Monomeric Silicon Disulfide Complex
Author(s) -
Xiong Yun,
Yao Shenglai,
Müller Robert,
Kaupp Martin,
Driess Matthias
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504489
Subject(s) - adduct , chemistry , lewis acids and bases , acetonitrile , monomer , carbene , sulfur , yield (engineering) , silicon , medicinal chemistry , nuclear magnetic resonance spectroscopy , crystal structure , elemental analysis , crystallography , stereochemistry , inorganic chemistry , organic chemistry , catalysis , materials science , metallurgy , polymer
The synthesis and characterization of the first bis‐N‐heterocyclic carbene stabilized monomeric silicon disulfide (bis‐NHC)SiS 2 2 (bis‐NHC=H 2 C[{NC(H)C(H)N(Dipp)}C:] 2 , Dipp=2,6‐ i Pr 2 C 6 H 3 ) 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 GaCl 3 in acetonitrile to give the corresponding (bis‐NHC)Si(S)S→GaCl 3 Lewis acid–base adduct 3 in 91 % yield. Compound 3 is also accessible through the reaction of the unprecedented silylone‐GaCl 3 adduct [(bis‐NHC)Si→GaCl 3 ] 4 with elemental sulfur. Compounds 2 , 3 , and 4 could be isolated and characterized by elemental analyses, HR‐MS, IR, 13 C‐ and 29 Si‐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 p π –p π bonding character.