Diphosphine‐Protected IrAu<sub>12</sub> Superatom with Open Site(s): Synthesis and Programmed Stepwise Assembly-Reference-Cited by-同舟云学术

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

Published:2024-02-28 Issue:18 Volume:63 Page:
ISSN:1433-7851
Container-title:Angewandte Chemie International Edition
language:en
Short-container-title:Angew Chem Int Ed

Author:

Fukumoto Yuto¹,Omoda Tsubasa¹²^ORCID,Hirai Haru¹^ORCID,Takano Shinjiro¹^ORCID,Harano Koji³^ORCID,Tsukuda Tatsuya¹^ORCID

Affiliation:

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.

Abstract

AbstractOne 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.

Funder

Japan Science and Technology Agency

Japan Society for the Promotion of Science

Publisher

Wiley

Link

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.202402025

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