Reactivity of a Disilyne RSi≡SiR (R = Si<i><sup>i</sup></i><sup></sup>Pr[CH(SiMe<sub>3</sub>)<sub>2</sub>]<sub>2</sub>) toward π-Bonds: Stereospecific Addition and a New Route to an Isolable 1,2-Disilabenzene
收藏资源简介：
The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with cis- and trans-butenes produced cis- and trans-3,4-dimethyl-1,2-disilacyclobutenes 2a and 2b, respectively. The reactions proceeded in a stereospecific manner. Theoretical calculations on the reaction between 1 and 2-butenes show that the reaction proceeds via the interaction between the LUMO (πin*) of 1 and the HOMO of 2-butene, resulting in a formal [1 + 2] cycloaddition to give the silacyclopropyl−silylene intermediate, followed by its ring expansion to produce the final product. The reaction of 1 with phenylacetylene produced 1,2-disilabenzene derivative as a mixture of the two regioisomers, one of them being characterized by X-ray crystallography. The six-membered ring of 1,2-disilabenzene of 3a is almost planar with an Si−Si bond length of 2.2018(18) Å and Si−C bond lengths of 1.804(4) and 1.799(5) Å.
