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One or two phenylacetylide (PA) ligand(s) were successfully removed from the IrAu12 superatomic core of [IrAu12(dppe)5(PA)2]+ (dppe = 1,2-bis(diphenylphosphino)ethane) by reaction with controlled amounts of tetrafluoroboric acid. Optical and nuclear magnetic resonance spectroscopies and density functional theory calculations revealed the formation of open Au site(s) on the IrAu12 core of [IrAu12(dppe)5(PA)1]2+ and [IrAu12(dppe)5]3+ with the remaining structure intact. Isocyanide was efficiently trapped at the open electrophilic site on [IrAu12(dppe)5(PA)1]2+, whereas a dimer or trimer of the IrAu12 superatoms was formed using diisocyanide as a linker. These results open the door to designed assembly of chemically modified metal superatoms.

Rights:

• Creative Commons BY-NC Attribution-NonCommercial 4.0 International
  

Keyword: ligand desorption reaction, superatoms, gold clusters, nanoclusters

Date published: 2024-04-24

Publisher: Wiley

Journal:

• Angewandte Chemie International Edition (ISSN: 00448249) vol. 63 issue. 18 e202402025

Funding:

• Japan Science and Technology Agency JPMJCR20B2
• Japan Society for the Promotion of Science JP20H00370
• Japan Society for the Promotion of Science JP23H00284
• Japan Society for the Promotion of Science JP23H01917
• Japan Society for the Promotion of Science JP23H04874

Manuscript type: Publisher's version (Version of record)

MDR DOI:

First published URL: https://doi.org/10.1002/anie.202402025

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Updated at: 2024-08-20 12:30:21 +0900

Published on MDR: 2024-08-20 12:30:21 +0900