Electronic Delocalization in Two and Three Dimensions: Differential Aggregation in Indium “Metalloid” Clusters

Reduction of indium boryl precursors to give two‐ and three‐dimensional M−M bonded networks is influenced by the choice of supporting ligand. While the unprecedented nanoscale cluster [In₆₈(boryl)₁₂]⁻ (with an In₁₂@In₄₄@In₁₂(boryl)₁₂ concentric structure), can be isolated from the potassium reduction of a bis(boryl)indium(III) chloride precursor, analogous reduction of the corresponding (benzamidinate)In^IIIBr(boryl) system gives a near‐planar (and weakly aromatic) tetranuclear [In₄(boryl)₄]²⁻ system.