title: From a Si3-Cyclopropene to a Si3S-Bicyclo[1.1.0]butane to a Si3S-Cyclopropene to a Si3S2-Bicyclo[1.1.0]butane: Back-and-Forth, and In-Between.
abstract: Compact and highly reactive bicyclo[1.1.0]butanes constitute one of the most fascinating classes of organic compounds. Furthermore, interplay of bicyclo[1.1.0]butanes with their valence isomers, such as buta-1,3-dienes and cyclobutenes, is among the fundamental pericyclic transformations in organic chemistry. Herein we report the back-and-forth interconversion between the cyclotrisilenes and thiatrisilabicyclo[1.1.0]butanes, allowing for the synthesis of novel representatives of such classes of highly reactive organometallics. The peculiar structural and bonding features of the newly synthesized compounds, as well as the mechanism of their isomerization, were verified both experimentally and computationally.
authors.affiliation: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8571, Ibaraki (Japan). leevya@chem.tsukuba.ac.jp.
authors.forename: Vladimir Ya
authors.initials: VY
authors.lastname: Lee
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachki Avenue, Rostov on Don 344090 (Russian Federation).
authors.forename: Olga A
authors.initials: OA
authors.lastname: Gapurenko
authors.affiliation: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8571, Ibaraki (Japan).
authors.forename: Shogo
authors.initials: S
authors.lastname: Miyazaki
authors.affiliation: Department of Chemistry, Graduate School of Pure and Applied Sciences, University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8571, Ibaraki (Japan). sekiguch@chem.tsukuba.ac.jp.
authors.forename: Akira
authors.initials: A
authors.lastname: Sekiguchi
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachki Avenue, Rostov on Don 344090 (Russian Federation).
authors.forename: Ruslan M
authors.initials: RM
authors.lastname: Minyaev
authors.affiliation: Institute of Physical and Organic Chemistry, Southern Federal University, 194/2 Stachki Avenue, Rostov on Don 344090 (Russian Federation).
authors.forename: Vladimir I
authors.initials: VI
authors.lastname: Minkin
authors.affiliation: CNRS, LCC, 205 Route de Narbonne, BP 44099 (France).|Université de Toulouse, UPS, INPT, 31077 Toulouse Cedex 4 (France).
authors.forename: Heinz
authors.initials: H
authors.lastname: Gornitzka
keywords: NMR spectroscopy; X-ray diffraction; cage compounds; computational chemistry; density functional calculations