Anionic and neutral clusters dominate the cluster chemistry of group 13 and 14 elements, many of which have become classic textbook examples of main group element clusters. However, facilitated by the development of unreactive, weakly coordinating anions, the number of known group 13 and 14 cationic cluster compounds has risen rapidly in recent years. Hence, this review aims to give an overview over this research field, which arouses increasing interest owing to the often unusual structures of the cationic clusters, as well as their application in bond activation chemistry. Challenges of the cluster formation are discussed and suitable starting materials are presented, as well as syntheses, structures and the rich follow-up chemistry of (also mixed) group 13 and 14 cluster cations.
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