Pure and Applied Chemistry

Abstract: This article highlights the achievements in the chemistry of supercarboranes (carboranes with more than 12 vertices) in the past decade and the future perspectives. The chemistry of boron clusters has been dominated by 12-vertex carboranes for several decades. Only in recent years has significant progress been made in the chemistry of supercarboranes. Such a breakthrough relies on the use of CAd (carbon-atoms-adjacent) 12-vertex nido-carborane anions as starting materials. A series of 13- and 14-vertex carboranes as well as their corresponding 14- and 15-vertex metallacarboranes have been prepared and structurally characterized. Reactions of supercarboranes with reducing agents, electrophiles, and nucleophiles are studied, which reveal a more diverse and richer reaction chemistry than their icosahedral cousins.