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

• Published in: Angewandte Chemie International Edition Vol. 56; no. 47; pp. 15098 - 15102
• Main Authors: Protchenko, Andrey V., Urbano, Juan, Abdalla, Joseph A. B., Campos, Jesús, Vidovic, Dragoslav, Schwarz, Andrew D., Blake, Matthew P., Mountford, Philip, Jones, Cameron, Aldridge, Simon
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 20-11-2017
• Edition: International ed. in English
• Subjects: boryl; gallium; Group 13 elements; Indium; metal cluster; Potassium; Reduction (metal working); indium; boryl; Group 13 elements; gallium; metal cluster
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201708496

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)InIIIBr(boryl) system gives a near‐planar (and weakly aromatic) tetranuclear [In4(boryl)4]2− system.
Clusters à la carte: Reduction of indium boryl complexes to give 2D and 3D aggregates can be controlled by the choice of supporting ligand. The unprecedented nanoscale cluster In12@In44@In12(boryl)12 (see picture) is isolated from the potassium reduction of a bis(boryl) precursor, while reduction of (amidinate)InIIIBr(boryl) gives a (weakly aromatic) planar tetranuclear [In4(boryl)4]2− system.