Abstract
The novel polyhedral closo‐Ga6 and Ga8 cluster ions [Ga6(R5)6]2– and [Ga8I4(R5)4]2– have been prepared as their lithium salts from reaction of the corresponding lithium silanide with a gallium subtriflate and “GaI”, respectively, together with the expected disproportionation products. All new compounds have been structurally characterized by single crystal X ray crystallography. The hexagallium cluster has a regular octahedral core, which is expected for a seven‐SEP cluster. The unexpected disphenoidal structure for the octagallium nine‐SEP cluster was compared to the square antiprismatic isomer by means of DFT calculations. In addition DFT calculations with dispersion correction on digallanes(4) R4Ga2 allow a new look on bonding in this gallium–gallium bonded compounds.
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