Closo‐decahydrodecaborate anion, [B10H10]2−, is one of the most notable clusters in the family of hydroborates, partly attributed to its unique electronic structure and its thermal and chemical stability. The major challenge in the development of [B10H10]2− chemistry resides in its functionalization via the activation of exo‐polyhedral B−H bonds to B−L bonds to generate attractive molecular construction modules or ‘archetypes’ of useful applications. To date, the closo‐[B10H10]2− cage has been functionalized with a wide range of functional groups ‐L such as halogens, amines, thiols, alkoxy, hydroxyl and multifunctional moieties to yield mono‐ or poly‐substituted borate derivatives. In this review, we present the recent trends in the chemistry of closo‐decaborate with focus on the substitution reactions of hydrogen atoms by various entities.
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