Electrochemistry with the extremely weak coordinating anions: Using of carboranes [H-CB11X6Y5]− (X = H, Cl, Br; Y = H or Me) as supporting electrolyte anions

• The utility of carborane anions as a new generation of supporting electrolytes is demonstrated.
• Application to the anodic processes of model organometallic complexes has been achieved.
• Similar results to those observed with [B(C6F5)4]− and [Al(OC(CF3)3)4]− are obtained.

This work demonstrates the feasibility of utilizing arguably the most inert, least basic, and extremely weak coordinating carborane anions, [H-CB11X6Y5]− (X = H, Cl, Br; Y = H or Me), as supporting electrolytes in low-polarity media. The redox behaviors of some model systems such as ferrocene (Fc), CoCp(CO)2 and [(η6-C6Me6)RhCp*]2 + in the presence of [NBu4][H-CB11H11], [NBu4][H-CB11Cl6Me5] and [NBu4][H-CB11Br6Me5] resemble those observed with other weakly coordinating anions (WCAs) such as [B(C6F5)4]− and [Al(OC(CF3)3)4]−. The overall results show that this class of carborane anions is a promising candidate for a new generation of WCA-based supporting electrolytes, for exploration the molecular electrochemistry of various organic, inorganic and organometallic compounds.

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