Synthesis and Structural Analysis of Organic Cyclic Polyselenides Obtained from the Reaction of a Bissilylcarbenoid with Selenium

The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane, obtained from the reaction of a bissilylcarbenoid ((R2CBrLi)-C-Si; R-Si=SiMePh2) with elemental selenium, is reported. The molecular structures of these cyclic polyselenides were determined using single-crystal X-ray diffraction analysis. The selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane with triphenylphosphine afforded the corresponding tetraselenolane in quantitative yield. Further deselenation of the tetraselenolane with excess triphenylphosphine did not furnish the expected selenoketone but the diselenirane, as confirmed by spectroscopic analysis.

Automated summary

The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane from the reaction of a bissilylcarbenoid with elemental selenium is reported. The molecular structures of these cyclic polyselenides were determined using X-ray diffraction analysis. Selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane yielded the tetraselenolane, while further deselenation of the tetraselenolane resulted in the formation of diselenirane.