Icosahedral m-Carboranes Containing Exopolyhedral B-Se and B-Te Bonds

Chalcogen-containing carboranes have been known for several decades and possess stable exopolyhedral B(9)-Se and B(9)-Te sigma bonds despite the electron-donating ability of the B(9) vertex. While these molecules are known, little has been done to thoroughly evaluate their electrophilic and nucleophilic behavior. Herein, we report an assessment of the electrophilic reactivity of m-carboranylselenyl(II), -tellurenyl(II), and -tellurenyl(IV) chlorides and establish their reactivity pattern with Grignard reagents, alkenes, alkynes, enolates, and electron-rich arenes. These electrophilic reactions afford unique electron-rich B-Y-C (Y = Se, Te) bonding motifs not commonly found before. Furthermore, we show that m-carboranylselenolate, and even m-carboranyltellurolate, can be competent nucleophiles and participate in nucleophilic aromatic substitution reactions. Arene substitution chemistry is shown to be further extended to electron-rich species via palladium-mediated cross-coupling chemistry.

Automated summary

This study evaluated the electrophilic and nucleophilic behavior of chalcogen-containing carboranes, revealing their unique bonding motifs. The compounds were found to participate in electrophilic reactions and act as competent nucleophiles in substitution reactions. Additionally, arene substitution chemistry was extended to electron-rich species via palladium-mediated cross-coupling reactions.