Monocarba-closo-dodecaborate (1; carborane anion) is a monoanionic boron cluster molecule with delocalized negative charge in the CB11 core, which results in the extremely low nucleophilicity/basicity. These characters have been utilized in the creation of superacids/isolation of unstable cationic species. Therefore, to control its physicochemical properties, versatile derivatization of carborane anion is very important. However, it has thus far been limited to simple substitution of the B/C-H bond such as methylation and halogenation. Thus, functionalization making use of oligomeric scaffolds has been almost unexplored area. We report herein a novel approach for the improvement of physicochemical characters of carborane scaffold based on the oligomeric strategies. Coupling of carborane anions between C1 vertices and linking of two carborane anions between B12 vertices with iodine/bromine (III) atom allow the synthesis of novel polyanionic/monoanionic dimers (2-6). These anions were analyzed by a combination of a DFT calculation and spectroscopic analysis. The detailed synthesis of these compounds and evaluation/applications of their unique properties will be presented.

New synthetic chemistry of monocarba-closo-dodecaborate based on oligomeric strategy

ACS Fall 2020 Virtual Meeting

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