Supraicosahedral Polyhedra in Metallaboranes: Synthesis and Structural Characterization of 12‑, 15‑, and 16-Vertex Rhodaboranes RoyDipak Kumar MondalBijan ShankhariPritam AnjuR. S. GeetharaniK. MobinShaikh M. GhoshSundargopal 2013 Syntheses and structural characterization of supraicosahedral rhodaborane clusters are reported. Reaction of [(Cp*RhCl<sub>2</sub>)<sub>2</sub>], (Cp* = η<sup>5</sup>-C<sub>5</sub>Me<sub>5</sub>) with [LiBH<sub>4</sub>·thf] followed by thermolysis with excess of [BH<sub>3</sub>·thf] afforded 16-vertex <i>closo</i>-[(Cp*Rh)<sub>3</sub>B<sub>12</sub>H<sub>12</sub>Rh­{Cp*RhB<sub>4</sub>H<sub>9</sub>}], <b>1</b>, 15-vertex [(Cp*Rh)<sub>2</sub>B<sub>13</sub>H<sub>13</sub>], <b>2</b>, 12-vertex [(Cp*Rh)<sub>2</sub>B<sub>10</sub>H<sub><i>n</i></sub>(OH)<sub><i>m</i></sub>], (<b>3a</b>: <i>n</i> = 12, <i>m</i> = 0; <b>3b</b>: <i>n</i> = 9, <i>m</i> = 1; <b>3c</b>: <i>n</i> = 8, <i>m</i> = 2) and 10-vertex [(Cp*Rh)<sub>3</sub>B<sub>7</sub>H<sub>7</sub>], <b>4</b>, and [(Cp*Rh)<sub>4</sub>B<sub>6</sub>H<sub>6</sub>], <b>5</b>. Cluster <b>1</b> is the unprecedented 16-vertex cluster, consists of a sixteen-vertex {Rh<sub>4</sub>B<sub>12</sub>} with an <i>exo</i>-polyhedral {RhB<sub>4</sub>} moiety. Cluster <b>2</b> is the first example of a carbon free 15-vertex supraicosahedral metallaborane, exhibits icosihexahedron geometry (26 triangular faces) with three degree-six vertices. Clusters <b>3a</b>-<b>c</b> have 12-vertex <i>isocloso</i> geometry, different from that of icosahedral one. Clusters <b>4</b> and <b>5</b> are attributed to the 10-vertex <i>isocloso</i> geometry based on 10-vertex bicapped square antiprism structure. In addition, quantum-chemical calculations with DFT methods at the BP86 level of theory have been used to provide further insight into the electronic structure and stability of the optimized structures which are in satisfactory agreement with the structure determinations. All the compounds have been characterized by IR, <sup>1</sup>H, <sup>11</sup>B, <sup>13</sup>C NMR spectroscopy in solution, and the solid state structures were established by crystallographic analysis of compounds <b>1</b>–<b>5</b>.