A series of novel isocloso-diiridaboranes [(Cp∗Ir)2B6H6], 1, 2; [1,7-(Cp∗Ir)2B8H8], 4; [1,4-(Cp∗Ir)2B8H8], 5; [(Cp∗Ir)2B9H9], 8; isonido-[(Cp∗Ir)2B7H7], 3; and 10-vertex cluster [5,7-(Cp∗Ir)2B8H12], 6 (Cp∗ = η5-C5Me5) have been isolated and structurally characterized from the pyrolysis of [Cp∗IrCl2]2 and BH3·thf. On the other hand, the corresponding rhodium system afforded 10- and 11-vertices clusters [5-(Cp∗Rh)B9H13)], 7, and [(Cp∗Rh)2B9H9], 9, respectively. Clusters 1 and 2 are topological isomers. The geometry of 1 is dodecahedral, similar to that of its parent borane [B8H8]2-, in which two of the [BH] vertices are replaced by two [Cp∗Ir] fragments. The geometry of 2 can be derived from a nine-vertex tricapped trigonal prism by removing one of the capped vertices. Compounds 4 and 5 are 10-vertex isocloso clusters based on a 10-vertex bicapped square antiprism structure. The only difference between them is the presence of a metal-metal bond in 5. The solid-state structures of 8 and 9 attain an 11-vertex geometry in which a unique six-membered B6H6 moiety is bonded to the metal center. In addition, quantum-chemical calculations have been used to provide further insight into the electronic structure and stability of the clusters. All the compounds have been characterized by IR and 1H, 11B, and 13C NMR spectroscopy in solution, and the solid-state structures were established by X-ray crystallographic analysis. © 2016 American Chemical Society.