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

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.