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A Tetrasilicon Analogue of Bicyclo[1.1.0]but‐1(3)‐ene Containing a Si=Si Double Bond with an Inverted Geometry
Author(s) -
Iwamoto Takeaki,
Abe Takashi,
Sugimoto Kunihisa,
Hashizume Daisuke,
Matsui Hiroshi,
Kishi Ryohei,
Nakano Masayoshi,
Ishida Shintaro
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201900824
Subject(s) - bicyclic molecule , propellane , ene reaction , double bond , molecular geometry , chemistry , bond length , silicon , crystallography , crystal structure , stereochemistry , molecule , polymer chemistry , organic chemistry
Bicyclo[1.1.0]tetrasil‐1(3)‐ene 1 , a tetrasilicon analogue of bicyclo[1.1.0]but‐1(3)‐ene that contains a formal double bond between bridgehead silicon atoms in an inverted geometry, was synthesized and isolated in the form of thermally stable orange crystals. The distance between the bridgehead Si atoms in 1 is much longer than those in typical Si=Si bonds, but still shorter than that of a previously reported pentasila[1.1.1]propellane. DFT calculations suggest that the bridgehead bond in 1 comprises a σ bond with an inverted geometry and a π bond. This notion is supported by the UV/Vis spectrum of 1 , which exhibits several absorption bands in the UV/Vis region. While 1 is stable toward typical trapping agents for Si=Si double bonds, 1 reacts with carbon tetrachloride to furnish a hexachlorotetrasilane.