Oxidative Perhydroxylation of [<i>closo</i>‐B₁₂H₁₂]²⁻ to the Stable Inorganic Cluster Redox System [B₁₂(OH)₁₂]^2−/.−: Experiment and Theory

Abstract

It′s radical: A surprisingly simple reaction converts the normally inert prototypical hydridoborate cluster [closo-B12H12]2− not only to [closo-B12(OH)12]2− but also, at less-elevated temperatures, to the new [hypocloso-B12(OH)12].− radical anion (see figure). Both approximately icosahedral closo and hypocloso cluster ions were structurally characterized as the cesium salts and their properties were assessed experimentally and theoretically.