Reaction of N‐Heterocyclic Silylenes with Thioketone: Formation of Silicon–Sulfur Three (Si‐C‐S)‐ and Five (Si‐C‐C‐C‐S)‐Membered Ring Systems |
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| Authors: | Dr. Ramachandran Azhakar Dr. Rajendra S. Ghadwal Prof. Dr. Herbert W. Roesky Prof. Dr. Ricardo A. Mata Hilke Wolf Regine Herbst‐Irmer Prof. Dr. Dietmar Stalke |
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| Affiliation: | 1. Institut für Anorganische Chemie der Universit?t G?ttingen, Tammannstrasse 4, 37077 G?ttingen (Germany);2. Institut für Physikalische Chemie der Universit?t G?ttingen, Tammannstrasse 6, 37077 G?ttingen (Germany) |
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| Abstract: | Three‐ and five‐membered rings that bear the (Si‐C‐S ) and (Si‐C‐C‐C‐S ) unit have been synthesized by the reactions of L SiCl ( 1 ; L =PhC(NtBu)2) and L′ Si ( 2 ; L′ =CH{(C?CH2)(CMe)(2,6‐iPr2C6H3N)2}) with the thioketone 4,4′‐bis(dimethylamino)thiobenzophenone. Treatment of 4,4′‐bis(dimethylamino)thiobenzophenone with L SiCl at room temperature furnished the [1+2]‐cycloaddition product silathiacyclopropane 3 . However, reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si at low temperature afforded a [1+4]‐cycloaddition to yield the five‐membered ring product 4 . Compounds 3 and 4 were characterized by NMR spectroscopy, EIMS, and elemental analysis. The molecular structures of 3 and 4 were unambiguously established by single‐crystal X‐ray structural analysis. The room‐temperature reaction of 4,4′‐bis(dimethylamino)thiobenzophenone with L′ Si resulted in products 4 and 5 , in which 4 is the dearomatized product and 5 is formed under the 1,3‐migration of a hydrogen atom from the aromatic phenyl ring to the carbon atom of the C? S unit. Furthermore, the optimized structures of probable products were investigated by using DFT calculations. |
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| Keywords: | cycloaddition density functional calculations silylenes small‐ring systems thioketones |
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