Diphosphine-Protected IrAu12 Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly

Yuto Fukumoto; Tsubasa Omoda; Haru Hirai; Shinjiro Takano; Koji Harano; Tatsuya Tsukuda

doi:10.1002/anie.202402025

Diphosphine-Protected IrAu₁₂ Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly

Angew Chem Int Ed Engl. 2024 Apr 24;63(18):e202402025. doi: 10.1002/anie.202402025. Epub 2024 Feb 28.

Authors

Yuto Fukumoto¹, Tsubasa Omoda^{1

2}, Haru Hirai¹, Shinjiro Takano¹, Koji Harano³, Tatsuya Tsukuda¹

Affiliations

¹ Department of Chemistry, Graduate School of Science, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
² Present address: Department of Chemical Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo, 152-8552, Japan.
³ Center for Basic Research on Materials, National Institute for Materials Science, 1-1 Namiki, Tsukuba, Ibaraki, 305-0044, Japan.

PMID: 38334176
DOI: 10.1002/anie.202402025

Abstract

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.

Keywords: ligand desorption reaction; phosphine-protected gold superatoms; programmed assembly.

Abstract

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