Direct Synthesis of <i>C</i>-Substituted [RC(O)CH₂-CB₁₁H₁₁]⁻ Carborate Anions

Abstract

A new synthetic method for the synthesis of C-substituted [RC(O)CH2-CB11H11]− carborate anions has been developed. The reaction of [closo-B11H11]2− with terminal alkynes in the presence of a copper catalyst leads to insertion into the boron cluster, and C-substituted [RC(O)CH2-CB11H11]− carborate anions are formed. These reactions are strongly dependent on the reaction conditions, the solvents, and the alkynes used. The alkynes HCCCO2Et, HCCCO2Me, and HCCCONH2 lead to the formation of [NH2C(O)CH2-CB11H11]− as the final product in aqueous ammonia solution. In contrast, the reaction using the alkyne HCCCOMe yields [MeC(O)CH2-CB11H11]−. The products have been fully characterized by multinuclear NMR and IR spectroscopy as well as mass spectrometry. The crystal structures of K[NH2C(O)CH2-CB11H11] and [NEt3CH2Cl][NH2C(O)CH2-CB11H11] have been determined.

Keywords

• acetamide
• boron cluster
• carborate
• <i>closo</i>-undecaborate