Isomeric Metamorphosis: Si<sub>3</sub>E (E = S, Se, and Te) Bicyclo[1.1.0]butane and\nCyclobutene
Vladimir Ya. Lee (1385730)Shogo Miyazaki (2451523)Hiroyuki Yasuda (1950334)Akira Sekiguchi (1385715)
Abstract
Group 14 and 16 hybrid heavy bicyclo[1.1.0]butanes (<i><sup>t</sup></i><sup></sup>Bu<sub>2</sub>MeSi)<sub>4</sub>Si<sub>3</sub>E (E = S, Se, and Te) <b>2a</b><b>−</b><b>c</b> have been prepared by the [1 + 2] cycloaddition reaction of trisilirene <b>1</b> and the corresponding chalcogen. Bicyclo[1.1.0]butanes <b>2</b> have exceedingly short bridging Si−Si bonds (2.2616(19) Å for <b>2b</b> and 2.2771(13) Å for <b>2c</b>), a phenomenon explained by the important contribution of the trisilirene−chalcogen π-complex character to the overall bonding of <b>2</b>. Photolysis of <b>2a</b> and <b>2b</b> produced their valence isomers, the heavy cyclobutenes <b>3a</b> and <b>3b</b>, featuring flat four-membered Si<sub>3</sub>E rings and a planar geometry of the SiSi double bond. The mechanism of such isomerization was studied using deuterium-labeled <b>2a</b>−<b><i>d</i></b><b><sub>6</sub></b> to ascertain the preference of the pathway, involving the direct concerted symmetry-allowed transformation of bicyclo[1.1.0]butane <b>2</b> to cyclobutene <b>3</b>.
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