Issue 27, 2021

Absolute configuration retention of a configurationally labile ligand during dynamic processes of thiolate protected gold clusters

Abstract

Monolayer protected metal clusters are dynamic nanoscale objects. For example, the chiral Au38(2-PET)24 cluster (2-PET: 2-phenylethylthiolate) racemizes at moderate temperature. In addition, ligands and metal atoms can easily exchange between clusters. Such processes are important for applications of monolayer protected metal clusters; however, the mechanistic study of such processes turns out to be challenging. Here we use a configurationally labile, axially chiral ligand, biphenyl-2,2′-dithiol (R/S-BiDi), as a probe to study dynamic cluster processes. It is shown that the ligand exchange of free R/S-BiDi on a chiral Au38(2-PET)24 cluster is diastereospecific. Using chiral chromatography, isolated single diastereomers of the type anticlockwise/clockwise-Au38(2-PET)22(R/S-BiDi)1 could be isolated. Upon heating, the cluster framework racemizes, while the R/S-BiDi ligand does not. These findings demonstrate that during cluster racemization and/or ligand exchange between clusters, the R/S-BiDi ligand is sufficiently confined, thus preventing its racemization, and exclude the possibility that the ligand desorbs from the cluster surface.

Graphical abstract: Absolute configuration retention of a configurationally labile ligand during dynamic processes of thiolate protected gold clusters

Supplementary files

Article information

Article type
Edge Article
Submitted
25 Mar 2021
Accepted
04 Jun 2021
First published
04 Jun 2021
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2021,12, 9413-9419

Absolute configuration retention of a configurationally labile ligand during dynamic processes of thiolate protected gold clusters

Y. Wang, E. Makkonen, X. Chen and T. Bürgi, Chem. Sci., 2021, 12, 9413 DOI: 10.1039/D1SC01702K

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