title: Monomeric siliconthiodichloride trapped by a Lewis base.
abstract: Thiophosgene (CSCl2), a chemical reagent used in numerous organic syntheses, exists in the monomeric form while its heavier silicon analogue [siliconthiodichloride (SiSCl2)] has been isolated so far as a dimer at room temperature and as a tetramer at 180 °C. Herein, we report on the first synthesis, isolation, and characterization of cyclic alkyl(amino) carbene (cAAC) stabilized siliconthiodichloride (cAAC)SiSCl2 (3) in the neutral monomeric form. 3 is synthesized via reaction of (cAAC˙)2Si2Cl4 (1) or (cAAC)2Si2Cl2 (2) with S8 in the temperature range of -78 to 20 °C. An NHC [NHC = N-heterocyclic carbene] analogue of 3 is not isolated when (NHC)SiCl2 is reacted with S8. The bright yellow colored compound 3 is soluble in polar organic solvents. It is stable at room temperature for a month under an inert atmosphere. 3 decomposes above 160 °C. The monomeric molecular structure of 3 has been unambiguously confirmed by X-ray single crystal diffraction. 3 is also characterized by NMR, UV-vis, and IR spectroscopy. The bonding and electron density distributions of 3 have been further studied by theoretical calculations.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany. hroesky@gwdg.de csdkartik@gmail.com.
authors.forename: Sudipta
authors.initials: S
authors.lastname: Roy
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany. hroesky@gwdg.de csdkartik@gmail.com.
authors.forename: Kartik Chandra
authors.initials: KC
authors.lastname: Mondal
authors.affiliation: Dept. of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur - 741246, India. koley@iiserkol.ac.in.
authors.forename: Totan
authors.initials: T
authors.lastname: Mondal
authors.affiliation: Dept. of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur - 741246, India. koley@iiserkol.ac.in.
authors.forename: Debasis
authors.initials: D
authors.lastname: Koley
authors.affiliation: Institut für Anorganische und Angewandte Chemie, Universität Hamburg, Raum AC 15c (Erdgeschoss), 20146 Hamburg, Germany. birger.dittrich@chemie.uni-hamburg.de.
authors.forename: Birger
authors.initials: B
authors.lastname: Dittrich
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, 37077 Göttingen, Germany. hroesky@gwdg.de csdkartik@gmail.com.
authors.forename: Herbert W
authors.initials: HW
authors.lastname: Roesky